WO2023181882A1

WO2023181882A1 - Analysis method, analysis device, management method for chemical solution, and management method for resist composition

Info

Publication number: WO2023181882A1
Application number: PCT/JP2023/008317
Authority: WO
Inventors: 正洋吉留; 暁彦大津
Original assignee: 富士フイルム株式会社
Priority date: 2022-03-24
Filing date: 2023-03-06
Publication date: 2023-09-28
Also published as: TW202401005A

Abstract

Provided is an analysis method capable of analysis of minute defects and reduction of measuring time, an analysis device, a management method for a chemical solution, and a management method for a resist composition. This analysis method for defects positioned on or in the interior of a semiconductor substrate comprises: a first step of setting a number of metal species to be analyzed; a second step of dividing an area to be measured of the semiconductor substrate into areas; a third step of assigning a different metal species to each of the divided areas; and a fourth step of irradiating each area with a laser, recovering an analysis sample resulting from the irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry.

Description

Analytical method, analytical device, chemical management method, and resist composition management method

The present invention relates to an analytical method for measuring metal elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), an analytical device, a chemical management method, and a resist composition management method, and particularly relates to The present invention relates to an analysis method, an analysis device, a chemical solution management method, and a resist composition management method for measuring metal elements by dividing a measurement region.

Currently, various semiconductor devices are manufactured using semiconductor substrates such as silicon substrates. If there are defects such as foreign objects on the surface of a semiconductor substrate, the semiconductor device manufactured may be defective due to insufficient formation of transistor gates or disconnection of wiring, etc. It may happen. As described above, defects such as foreign particles on the surface of a semiconductor substrate affect the yield of semiconductor devices.

Regarding defects in semiconductor substrates, for example, there is a method for evaluating metal contamination of wafers disclosed in Patent Document 1, which non-destructively evaluates defects in semiconductor substrates.
The method for evaluating metal contamination on a wafer in Patent Document 1 includes a light scattering particle counter that detects foreign matter by scanning the wafer surface with a laser beam and measuring the intensity of light scattering from the foreign matter as a foreign matter inspection device. (for example, SurfScan SP5 manufactured by KLA Corporation), and a laser microscope with a confocal optical system that detects foreign objects by detecting the difference in reflected light from the wafer surface (for example, MAGICS manufactured by Lasertec Corporation). Are listed. In Patent Document 1, a bright spot is observed using a SEM (Scanning Electron Microscope) based on the coordinates obtained in the first step, and EDX (Energy dispersive X-ray spectroscopy) is performed based on characteristic X-rays generated by electron beam irradiation. ) It is stated that the analysis will be performed.

JP2020-027920A

In Patent Document 1, SEM observation of bright spots is performed for each wafer based on the coordinates obtained in the first step, and EDX analysis is performed based on the characteristic X-rays generated by electron beam irradiation, so the operation is easy. It is complicated and tends to take a long time to measure. Furthermore, as the number of metal species detected in EDX analysis increases, the measurement time becomes even longer.
Here, as mentioned above, if there are defects such as foreign particles on the surface of the semiconductor substrate, the defects on the surface of the semiconductor substrate will become more serious, especially as semiconductor devices become smaller and more highly integrated. , the production of defective semiconductor devices will occur, which will have a significant impact on yield deterioration. For this reason, it is important to measure defects on the surface of a semiconductor substrate, and among defects on a semiconductor substrate, measurement of microscopic foreign particles is even more important.
However, when the method for evaluating metal contamination of a wafer described in Patent Document 1 is used to analyze minute foreign particles of about 20 nm on the surface of a semiconductor substrate, there is a high possibility that elemental analysis cannot be performed with EDX. Currently, there is a demand for analysis of even smaller defects, and a device that can analyze minute foreign particles of about 20 nm on the surface of a semiconductor substrate is desired.

An object of the present invention is to provide an analysis method, an analysis device, a chemical solution management method, and a resist composition management method that enable analysis of minute defects and shorten measurement time.

In order to achieve the above object, the invention [1] provides a method for analyzing defects located on or inside a semiconductor substrate, which includes a step 1 of setting the number of metal species to be analyzed, and a measurement target area of the semiconductor substrate. step 2 of dividing the area into regions, step 3 of assigning a different metal type to each divided region, irradiating each region with laser light, collecting the analytical sample obtained from the irradiation with a carrier gas, and guiding it. This is an analysis method comprising a step 4 of performing coupled plasma mass spectrometry.
Invention [2] is a method for analyzing defects located on or inside a semiconductor substrate, which includes determining the number of metal species to be analyzed, dividing a region to be measured, and each divided region on the semiconductor substrate. irradiating each region with laser light based on setting information including the metal species assigned to the area, collecting the analysis sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry. It's a method.

Invention [3] is the analysis method according to invention [1], which includes a step of obtaining contour information on the surface of the semiconductor substrate and obtaining information on the measurement target region before step 2.
Invention [4] is the analysis method according to any one of inventions [1] to [3], wherein 4 to 10 metal species are measured per region of the semiconductor substrate.
Invention [5] is the analysis method according to any one of inventions [1] to [3], wherein two or three metal species are measured per region of the semiconductor substrate.
Invention [6] is the analysis method according to any one of inventions [1] to [3], wherein one metal species is measured per region of the semiconductor substrate.
Invention [7] is the method according to any one of inventions [1] and [3] to [6], wherein step 1 of setting the number of metal types to be analyzed includes a step of setting the number of metal types to be analyzed. Analysis method.
Invention [8] is the analysis method according to any one of inventions [2] and [4] to [6], wherein the setting information includes information on the metal species to be analyzed.

Invention [9] is an apparatus for analyzing defects located on or inside a semiconductor substrate, in which the number of metal species to be analyzed is set, the measurement target area of the semiconductor substrate is divided into regions, and each divided region is , an analysis device that has a setting section that assigns different metal types, and an analysis section that irradiates each region with laser light, collects the analysis sample obtained from the irradiation with a carrier gas, and performs inductively coupled plasma mass spectrometry. .
Invention [10] is an apparatus for analyzing defects located on or inside a semiconductor substrate, which analyzes the semiconductor substrate by determining the number of metal species to be analyzed, dividing a region to be measured, and each divided region. an analysis section that irradiates each region with a laser beam based on setting information including the metal species assigned to the area, collects an analysis sample obtained from the irradiation with a carrier gas, and performs inductively coupled plasma mass analysis; It is an analytical device.

Invention [11] is the analysis device according to invention [9], which includes an alignment measurement unit that obtains contour information on the surface of the semiconductor substrate and obtains information on the measurement target region.
Invention [12] is the analysis device according to Invention [9] or [11], wherein the setting unit sets the number of metal types per region of the semiconductor substrate to 4 to 10.
Invention [13] is the analysis device according to Invention [9] or [11], wherein the setting unit sets the number of metal types per region of the semiconductor substrate to 2 or 3.
Invention [14] is the analysis device according to Invention [9] or [11], wherein the setting unit sets the metal type per region of the semiconductor substrate to 1.
Invention [15] is the analyzer according to any one of inventions [9] and [11] to [14], wherein the setting section sets the metal species to be analyzed.
Invention [16] is the analysis device according to invention [10], wherein the setting information includes information on the metal species to be analyzed.

Invention [17] is a method for managing a chemical solution, which includes a step of bringing a semiconductor substrate into contact with a chemical solution, a step of setting the number of metal species to be analyzed, and a step of dividing a measurement target region of the semiconductor substrate into regions. A process of assigning a different metal type to each divided area, a process of irradiating each area with laser light, collecting the analysis sample obtained from the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry; A process of comparing mass spectrometry data of defects obtained in the process of coupled plasma mass spectrometry with preset reference data to determine whether the mass spectrometry data is within an acceptable range. It is a management method.
Invention [18] is a method for managing a chemical solution, which includes a step of bringing a semiconductor substrate into contact with a chemical solution, determining the number of metal species to be analyzed on the semiconductor substrate, dividing a region to be measured, and dividing the semiconductor substrate into regions. irradiating each region with a laser beam based on setting information including the metal type assigned to each region, collecting an analysis sample obtained from the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry; A chemical solution comprising a step of comparing mass spectrometry data of defects obtained in the step of inductively coupled plasma mass spectrometry with preset reference data to determine whether the mass spectrometry data is within an acceptable range. This is a management method.
Invention [19] is the method according to invention [17], which includes a step of obtaining contour information on the surface of the semiconductor substrate and obtaining information on the measurement target region before the step of dividing the measurement target region of the semiconductor substrate into regions. How to manage chemical solutions.
Invention [20] is the method for managing a chemical solution according to Invention [17] or [19], wherein the step of setting the number of metal species to be analyzed includes a step of setting the metal species to be analyzed.
Invention [21] is the method for managing a chemical solution according to invention [18], wherein the setting information includes information on the metal species to be analyzed.

Invention [22] is a method for managing a resist composition, which includes a step of applying a resist composition onto a semiconductor substrate, a step of setting the number of metal species to be analyzed, and a step of dividing a measurement target region of the semiconductor substrate into regions. a step of assigning a different metal type to each divided region, a step of irradiating each region with laser light, collecting the analysis sample obtained from the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry. and a step of comparing mass spectrometry data of defects obtained in the process of inductively coupled plasma mass spectrometry with preset reference data to determine whether the mass spectrometry data is within an acceptable range. This is a method for managing a resist composition.
Invention [23] is a method for managing a resist composition, which includes the steps of applying the resist composition onto a semiconductor substrate, the number of metal species to be analyzed, and region division of a measurement target region on the semiconductor substrate. Based on the setting information including the metal species assigned to each divided region, each region is irradiated with laser light, the analysis sample obtained from the irradiation is collected with a carrier gas, and inductively coupled plasma mass spectrometry is performed. and a step of comparing the mass spectrometry data of the defect obtained in the process of inductively coupled plasma mass spectrometry with preset reference data to determine whether the mass spectrometry data is within an acceptable range. A method for managing a resist composition.
Invention [24] is the method according to invention [22], which includes a step of obtaining contour information on the surface of the semiconductor substrate and obtaining information on the measurement target region before the step of dividing the measurement target region of the semiconductor substrate into regions. How to manage resist composition.
Invention [25] is the method for managing a resist composition according to invention [22] or [24], wherein the step of setting the number of metal species to be analyzed includes a step of setting the metal species to be analyzed.
Invention [26] is the resist composition management method according to Invention [23], wherein the setting information includes information on the metal species to be analyzed.The setting information includes information on the metal species to be analyzed.

According to the present invention, it is possible to provide an analysis method, an analysis device, a chemical solution management method, and a resist composition management method that can shorten measurement time.

FIG. 1 is a schematic diagram showing a first example of an analysis device according to an embodiment of the present invention. FIG. 2 is a schematic diagram showing a first example of region division of a semiconductor substrate in a first example of an analysis device according to an embodiment of the present invention. FIG. 7 is a schematic diagram showing a second example of region division of a semiconductor substrate in the first example of the analysis device according to the embodiment of the present invention. FIG. 7 is a schematic diagram showing a third example of region division of a semiconductor substrate in the first example of the analysis device according to the embodiment of the present invention. It is a schematic diagram showing an example of the analysis unit of the 1st example of the analysis device of the embodiment of the present invention. FIG. 1 is a schematic cross-sectional view illustrating a first example of an analysis method according to an embodiment of the present invention. 1 is a flowchart showing a first example of an analysis method according to an embodiment of the present invention. FIG. 2 is a schematic diagram showing a second example of an analysis device according to an embodiment of the present invention. 1 is a flowchart illustrating an example of a method for managing a chemical solution according to an embodiment of the present invention. 1 is a flowchart illustrating an example of a resist composition management method according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The analysis method, analysis device, chemical solution management method, and resist composition management method of the present invention will be described in detail below based on preferred embodiments shown in the accompanying drawings.
Note that the figures described below are illustrative for explaining the present invention, and the present invention is not limited to the figures shown below.
In addition, in the following, "~" indicating a numerical range includes the numerical values written on both sides. For example, when ε is a numerical value ε _α to a numerical value ε _β , the range of ε is a range that includes the numerical value ε _α and the numerical value ε _β , and expressed in mathematical symbols as ε _α ≦ε≦ε _β .
Unless otherwise specified, angles such as "angle expressed in specific numerical values", "parallel", "perpendicular", and "perpendicular" include error ranges generally accepted in the relevant technical field.
Furthermore, "same" includes a generally acceptable error range in the relevant technical field. In addition, "entire surface" and the like include the error range generally allowed in the relevant technical field.

[First example of analysis device]
FIG. 1 is a schematic diagram showing a first example of an analyzer according to an embodiment of the present invention, and FIG. 2 is a schematic diagram showing an example of an analysis unit of the first example of an analyzer according to an embodiment of the present invention. .
The analyzer 10 shown in FIG. 1 includes an alignment measurement section 20, a storage section 26, a calculation section 27, a setting section 28, an input section 29, and an analysis section 30, which will be described in detail later.
The analysis device 10 analyzes defects located on or inside the surface 50a of the semiconductor substrate 50, using the semiconductor substrate 50 as a measurement target. A method for analyzing defects located on or inside a semiconductor substrate using the analyzer 10 will be described later, but the analyzer used in the analysis method is not particularly limited to the analyzer 10 shown in FIG. , other configurations of analyzers can be used.

The analyzer 10 has a first transfer chamber 12a, a measurement chamber 12b, a second transfer chamber 12c, and an analysis chamber 12d. are arranged consecutively in order. The first transfer chamber 12a, the measurement chamber 12b, the second transfer chamber 12c, and the analysis chamber 12d are each partitioned by a wall 12h. ) etc., and the door may be opened when the semiconductor substrate 50 is passed through. Although the measurement chamber 12b and the second transfer chamber 12c are arranged in succession, the present invention is not limited to this, and a load lock chamber may be provided between the measurement chamber 12b and the second transfer chamber 12c.

In the analyzer 10, the semiconductor substrate 50 is transported from outside the analyzer 10 to the first transport chamber 12a, and is transported from the first transport chamber 12a to the measurement chamber 12b, and is then processed by the alignment measuring section 20 within the measurement chamber 12b. , the contour of the surface 50a of the semiconductor substrate 50 is measured, and contour information of the surface 50a of the semiconductor substrate 50 is obtained. From this contour information, the shape of the surface 50a of the semiconductor substrate 50 is specified, and the measurement target area of the semiconductor substrate 50 is specified. Thereby, information on the measurement target area of the semiconductor substrate 50 can be obtained. The measurement target area of the semiconductor substrate 50 is an area surrounded by the outline of the surface 50a of the semiconductor substrate 50 to be analyzed.
Here, the contour information is expressed, for example, by two-dimensional position coordinates set with respect to the surface 50a of the semiconductor substrate 50. The positional coordinates are set, for example, with the center position of the surface 50a of the semiconductor substrate 50 as the origin. In this case, a reference is set for each semiconductor substrate 50. In addition to this, for example, a reference point can be provided on the stage 22, and the contour information of the surface 50a of the semiconductor substrate 50 can be expressed as position coordinates using this reference point as the origin. In this way, a reference position common to a plurality of semiconductor substrates 50 can be set in advance, and two-dimensional position coordinates of contour information can be expressed using the reference position as the origin.
Further, information on the measurement target region of the semiconductor substrate 50 is also expressed, for example, in two-dimensional position coordinates, similar to the contour information.

Furthermore, in addition to the above-mentioned contour information, information on the center position of the semiconductor substrate 50 can also be obtained. The information on the center position of the semiconductor substrate 50 is the position information on the geometric center of the two-dimensional shape obtained from the contour information on the surface 50a of the semiconductor substrate 50. Information on the center position of the semiconductor substrate 50 can be obtained, for example, by determining position information on the geometric center of a two-dimensional shape obtained from contour information on the surface 50a of the semiconductor substrate 50. Information on the center position of the semiconductor substrate 50 is also expressed in two-dimensional position coordinates.
Contour information on the surface 50a of the semiconductor substrate 50, information on the measurement target area, and information on the center position of the semiconductor substrate 50 are stored in the storage unit 26. Further, the number of metal species to be analyzed is set, the measurement target region of the semiconductor substrate 50 is divided into regions, and a different metal species is assigned to each divided region. Note that each divided area is also represented by two-dimensional position coordinates. Further, the number of metal species to be analyzed that is set is also referred to as the total number of metal species that are set to be analyzed. This is to distinguish from the number of metal species set in each region.

Next, the semiconductor substrate 50 whose contour information has been acquired is transported from the measurement chamber 12b to the second transport chamber 12c, and further transported to the analysis chamber 12d. Information on the measurement target area based on contour information of the surface 50a of the semiconductor substrate 50 obtained by the alignment measurement unit 20, information on each area obtained by dividing the measurement area of the semiconductor substrate 50, and measurement in each area. The analysis unit 30 analyzes the surface defects of the semiconductor substrate 50 based on the information on the metal species.
In the analyzer 10, in order to prevent the semiconductor substrate 50 from being exposed to the outside air, the interiors of the first transfer chamber 12a, measurement chamber 12b, second transfer chamber 12c, and analysis chamber 12d can be set to a specific atmosphere. . For example, a vacuum pump may be provided to exhaust the gas inside the first transfer chamber 12a, measurement chamber 12b, second transfer chamber 12c, and analysis chamber 12d to create a reduced pressure atmosphere. Alternatively, an inert gas such as nitrogen gas may be supplied inside the first transfer chamber 12a, measurement chamber 12b, second transfer chamber 12c, and analysis chamber 12d to create an inert gas atmosphere inside.

As described above, the first transfer chamber 12a transfers the semiconductor substrate 50 transferred from the outside of the analyzer 10 to the measurement chamber 12b. The first transfer chamber 12a is provided with an introduction section 12g on the side surface. A storage container 13 is installed in the introduction section 12g. A sealing member (not shown) is provided in the introduction part 12g to maintain airtightness with the storage container 13.
For example, the storage container 13 stores therein a plurality of semiconductor substrates 50 arranged in a shelf-like manner. The semiconductor substrate 50 is, for example, a disk-shaped substrate.
The storage container 13 is, for example, a FOUP (Front Opening Unified Pod). By using the storage container 13, the semiconductor substrate 50 can be transported to the analyzer 10 in a sealed state without being exposed to the outside air. Thereby, contamination of the semiconductor substrate 50 can be suppressed.

A transport device 14 is provided inside the first transport chamber 12a. The transport device 14 transports the semiconductor substrate 50 in the storage container 13 from the first transport chamber 12a to the adjacent measurement chamber 12b.
The transport device 14 is not particularly limited as long as it can take out the semiconductor substrate 50 from the storage container 13 and transport it to the stage 22 of the measurement chamber 12b.
The transport device 14 shown in FIG. 1 includes a transport arm 15 that holds the outside of the semiconductor substrate 50, and a drive section (not shown) that drives the transport arm 15. The transport arm 15 is attached to the attachment part 14a and is rotatable around the rotation axis _C1 . Note that the configuration of the transfer arm 15 is not particularly limited to one that holds the outside of the semiconductor substrate 50 as long as it can hold and transfer the semiconductor substrate 50, and the structure is not particularly limited to one that holds the outside of the semiconductor substrate 50. Those used for transportation can be used as appropriate.
In the conveyance device 14, the mounting portion 14a can move in the height direction V, and the conveyance arm 15 can move in the height direction V, which is a direction parallel to the rotation axis _C1 . By moving the mounting portion 14a in the height direction V, the position of the transport arm 15 in the height direction V can be changed.

(Alignment measurement section)
An alignment measurement section 20 is provided in the measurement chamber 12b. The alignment measuring section 20 detects the contour of the surface 50a of the semiconductor substrate 50 and obtains contour information of the surface 50a of the semiconductor substrate 50. The alignment measurement section 20 is connected to a calculation section 27 and a storage section 26.
The alignment measuring section 20 includes a stage 22 on which the semiconductor substrate 50 is placed, a light source 23 that irradiates the surface 50a of the semiconductor substrate 50 with light Ls, and an imaging section 24 that observes the semiconductor substrate 50.
The stage 22 on which the semiconductor substrate 50 is placed is rotatable around the rotation axis _C2 , and can change the position of the semiconductor substrate 50 in the height direction V, and can change the position of the semiconductor substrate 50 in the direction H perpendicular to the height direction V. Can change position. The stage 22 allows the position of the semiconductor substrate 50 with respect to the imaging section 24 to be adjusted.

The wavelength of the light Ls emitted by the light source 23 is not particularly limited. The light Ls is, for example, ultraviolet light, but may also be visible light or other light. Here, ultraviolet light refers to light in a wavelength range of less than 400 nm, and visible light refers to light in a wavelength range of 400 to 800 nm.
Here, when all horizontal directions are 0° and the direction perpendicular to the surface 50a of the semiconductor substrate 50 is 90°, the incident angle of the light Ls is particularly limited as long as the surface 50a of the semiconductor substrate 50 can be irradiated. It's not a thing.

The imaging unit 24 is configured to image the outline of the front surface 50a of the semiconductor substrate 50, and can image a region including the outline of the front surface 50a of the semiconductor substrate 50.
Moreover, if the semiconductor substrate 50 has an alignment mark, it is preferable that the imaging unit 24 can image the alignment mark. Further, when the semiconductor substrate 50 has a notch, an orientation flat, or an alignment mark, it is preferable that the notch, orientation flat, and alignment mark can be imaged. The imaging unit 24 preferably includes, for example, a CCD (Charge Coupled Devices) element or a CMOS (Complementary Metal Oxide Semiconductor) element, and has a number of pixels capable of performing the various types of imaging described above.
Further, the number of imaging units 24 is not limited to one, and may be plural.
Incidentally, as long as the image capturing section 24 can image the outline of the surface 50a of the semiconductor substrate 50, the irradiation of the light Ls by the light source 23 is not necessarily necessary.

The imaging unit 24 is connected to a storage unit 26 , and image data including contour information obtained by the imaging unit 24 is output to and stored in the storage unit 26 .
The calculation unit 27 reads the image data of the semiconductor substrate 50 stored in the storage unit 26, and the calculation unit 27 specifies the shape of the surface 50a of the semiconductor substrate 50 from the contour information as described above. A measurement target area is specified. As a result, information on the measurement target region of the semiconductor substrate 50 can be obtained.
Note that when the contour information of the surface 50a of the semiconductor substrate 50 is insufficient, the calculation unit 27 calculates contour information by complementing the contour information of the surface 50a of the semiconductor substrate 50 from the obtained contour information. It's okay.
In addition, the calculation unit 27 specifies the two-dimensional position coordinates of the contour information of the surface 50a of the semiconductor substrate 50, and determines the information on the center position of the semiconductor substrate 50, that is, the position of the geometric center of the two-dimensional shape obtained from the contour information. get information. Thereby, the placement position of the semiconductor substrate 50 on the stage 22 can be specified. Furthermore, the placement position of the semiconductor substrate 50 on the stage 22 can be specified.
If the semiconductor substrate 50 has a notch, orientation flat, or alignment mark, the calculation unit 27 can also specify the positional relationship between the notch, orientation flat, or alignment mark and the center position of the semiconductor substrate 50.
The storage unit 26 stores contour information on the surface 50a of the semiconductor substrate 50, information on the measurement target area, information on the position of a notch, orientation flat, or alignment mark, and information on the center position of the semiconductor substrate 50.

Here, the setting unit 28 sets the number of metal species to be analyzed. Further, the measurement target region of the semiconductor substrate 50 is divided into regions, and a different metal type is assigned to each divided region. The measurement target area obtained by the alignment measuring section 20 as described above may be used as the measurement target area. If there is information on the measurement target area of the semiconductor substrate 50 to be analyzed in advance, instead of the measured value, the information on the measurement target area can also be used. In the setting unit 28, the relationship between the number of metal species to be analyzed and the number of regions may be set in advance, and the number of regions may be determined from the number of metal species to be analyzed based on this. In addition, the relationship between the number of metal species to be analyzed, the number of regions, and the number of metal species assigned to the regions is set in advance, and based on this, the number of regions and the number of regions can be changed from the number of metal species to be analyzed. The number of metal species to be assigned may be determined.
The number of metal species to be analyzed is preferably 2 or more, more preferably 10 or more, even more preferably 20 or more, and even more preferably 30 or more. Note that the upper limit of the number of metal species to be analyzed is not particularly limited, but is appropriately determined depending on the performance of the analysis unit 36, analysis time, etc., which will be described later.

Note that the setting unit 28 assigns different metal types to each region divided as described above. The meaning of "assigning different metal species" means that when the two divided regions are compared, the types of metal species to be assigned do not completely match. In other words, for example, when comparing two divided areas, if one metal type is assigned to each area, if the metal types assigned to each area are different, it will be This corresponds to "assigning a metal type".
Also, for example, when comparing two divided regions, if two or more metal types are assigned to each region, even if some metal types overlap in the two regions, each It is assumed that different metal types are assigned unless the metal types included in the region are exactly the same. More specifically, if Fe, Li, and Na are assigned to region A and Fe, Cu, and Pd are assigned to region B, Fe overlaps, but in region A and region B, three types of Since the types of metal species do not completely match, it is assumed that different metal types are assigned.
Further, when assigning different metal types, it is not limited to assigning the same number of metal types to each area, and the number of metal types may be different in each area.
Note that, from the above, the setting unit 28 sets a different metal type in each divided area, but it may also be set so that the metal types do not overlap in each area, and the metal type in each area can be set so that the metal types do not overlap. Some of the metal types may be set to be duplicated, except that they completely match.

Further, in the calculation unit 27, in each area of the semiconductor substrate 50, based on the information of each divided area of the semiconductor substrate 50 described above set by the setting unit 28 and the information of the measurement target area of the semiconductor substrate, The range to be irradiated with laser light and the position coordinates of that range are calculated. The calculation unit 27 further determines the range to be irradiated with the laser beam La and the metal type to be measured in the range to be irradiated with the laser beam La, and obtains combination data of the range to be irradiated with the laser beam La and the metal type to be measured. obtain. The calculation unit 27 causes the storage unit 26 to store the combination data.
In addition, the control unit 42 controls the analysis unit 36 based on the information on the metal species assigned to each divided region, that is, the above-mentioned combination data, and makes settings for each divided region. conduct an analysis of the metal species.

The input section 29 is used to input setting information set in the setting section 28, which will be described later. The input unit 29 may be an interface such as a keyboard and a mouse, or may be a device that reads a recording medium such as a memory card reader. Moreover, when the setting information is transmitted via wireless or the Internet, the input section 29 has a receiving section that receives wireless signals, or can be connected to the Internet.
Here, the setting information is information including the number of metal species to be analyzed, the region division of the measurement target region, and the metal species assigned to each of the divided regions. Further, the setting information may include information on the type of metal to be analyzed. Information on metal species to be analyzed includes elemental species that can be measured by LA-ICP-MS. Information on the metal species to be analyzed includes, for example, Li, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, Hf, Ta, W, Re, TI, Pb, Bi, Po, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr are the metal elements to be detected.
The input format of the setting information is not particularly limited, and the setting information may be input into the setting unit 28 using an interface such as a keyboard, or the setting information may be read or received by the setting unit 28.

As described above, the storage unit 26 stores information on the outline of the surface 50a of the semiconductor substrate 50, information on the measurement target area, information on the position of the notch, orientation flat, or alignment mark, information on the center position of the semiconductor substrate 50, etc. If possible, various storage media such as volatile memory, non-volatile memory, hard disk, or SSD (Solid State Drive) can be used without particular limitation. Furthermore, the storage unit 26 may be a storage medium placed on a cloud.

The calculation unit 27 and the setting unit 28 may be configured by, for example, a computer in which each part functions by executing a program or computer software, or may be a dedicated device in which each part is configured with a dedicated circuit. , may be configured on a server to run on the cloud. In addition, for the analysis method, a program or computer software may be used, a dedicated device configured with a dedicated circuit may be used, and a server may be used for the analysis method so as to be executed on the cloud. .

Here, in the alignment measuring section 20, the stage 22, the light source 23, and the imaging section 24 are controlled by the control section 42. Furthermore, the storage section 26 and the calculation section 27 are also controlled by the control section 42 .
For example, the control unit 42 causes the light source 23 to irradiate the surface 50a of the semiconductor substrate 50 with light Ls, the imaging unit 24 images the semiconductor substrate 50, and the image data including contour information obtained by the imaging unit 24 is stored in the storage unit. 26 and stored. The calculation unit 27 reads the image data from the storage unit 26, and specifies the two-dimensional position coordinates of the contour information on the surface 50a of the semiconductor substrate 50.
At the time of measurement by the alignment measurement section 20, the atmosphere in the measurement chamber 12b is not particularly limited, and may be a reduced pressure atmosphere or a nitrogen gas atmosphere as described above.

A transport device 16 is provided inside the second transport chamber 12c. The transport device 16 transports the semiconductor substrate 50 whose contour information has been measured by the alignment measuring section 20 in the measurement chamber 12b from the measurement chamber 12b to the analysis chamber 12d.
The transport device 16 may have the same configuration as the transport device 14 described above. The transport device 16 includes a transport arm 15 that holds the outside of the semiconductor substrate 50, and a drive section (not shown) that drives the transport arm 15. The transport arm 15 is attached to the attachment part 16a and is rotatable around the rotation axis _C1 .
In the conveying device 16, the mounting portion 16a is movable in the height direction V, which is a direction parallel to the rotation axis _C1 . The position of the transport arm 15 in the height direction V can be changed by moving the mounting portion 16a to which the transport arm 15 is attached in the height direction V.

In the analyzer 10, the measurement target region of the semiconductor substrate 50 is divided into regions. The method of dividing the measurement target region into regions is not particularly limited.
Here, FIG. 2 is a schematic diagram showing a first example of region division of a semiconductor substrate in a first example of an analysis apparatus according to an embodiment of the present invention, and FIG. FIG. 4 is a schematic diagram showing a second example of region division of the semiconductor substrate in Example 1, and FIG. 4 shows a third example of region division of the semiconductor substrate in the first example of the analysis device according to the embodiment of the present invention. It is a schematic diagram.
For example, as shown in FIG. 2, the surface 50a of the semiconductor substrate 50 is divided into fan-shaped regions having a central position O at the apex. In FIG. 2, it is divided into eight fan-shaped regions 52a to 52h, and the eight fan-shaped regions 52a to 52h are in a congruent relationship. The center angles of the eight fan-shaped regions 52a to 52h are the same. The position coordinates are specified for each of the fan-shaped regions 52a to 52h, and a laser beam is irradiated to each region corresponding to the fan-shaped regions 52a to 52h on the surface 50a of the semiconductor substrate 50, so that the metal set for each region is A seed analysis is performed and defects 51 (see FIG. 1) are analyzed.
Note that, as shown in FIG. 2, dividing into fan-shaped regions 52a to 52h having a common center is also called cake cutting. The fan-shaped regions 52a to 52h are also expressed by two-dimensional position coordinates.
The number of divisions of the front surface 50a of the semiconductor substrate 50 is not limited to eight, but is at least two. The upper limit of the number of divisions is not particularly limited, but considering the measurement time, the upper limit of the number of divisions is 30.
Note that evaluation stability is improved by ensuring a sufficient measurement area. Therefore, in the case of a semiconductor wafer with a diameter of 12 inches, the lower limit of the measurement area per metal element to be measured is preferably 24 cm ² , a more preferable area is 71 cm ² or more and 236 cm ² or less, and the most preferable area is more than 236 cm ² Less than 706.5 ^cm2 .
Further, the sizes of the fan-shaped regions 52a to 52h are not limited to being all the same, and may be different in size. That is, the central angles of the fan-shaped regions 52a to 52h may be different.

Although the surface 50a of the circular semiconductor substrate 50 is divided into fan-shaped regions as shown in FIG. 2, the present invention is not limited to this. For example, as shown in FIG. The area may be divided by a line 53 parallel to the straight line passing through the center position O. In this case, in FIG. 3, the surface 50a of the semiconductor substrate 50 is divided into four regions 53a to 53d at equal intervals along the diameter direction. The position coordinates are specified for each of the four regions 53a to 53d, and each region corresponding to the four regions 53a to 53d on the surface 50a of the semiconductor substrate 50 is irradiated with a laser beam to determine the metal type set for each region. An analysis is performed and defects 51 are analyzed.
Note that, as shown in FIG. 3, dividing the circular semiconductor substrate 50 into a plurality of regions by a line 53 parallel to a straight line passing through the center position O is also referred to as vertical division. The four regions 53a to 53d described above are also represented by two-dimensional position coordinates.
The number of divisions of the front surface 50a of the semiconductor substrate 50 is not limited to four, but is at least two. In the two cases, FIGS. 2 and 3 match in area. The upper limit of the number of divisions is not particularly limited, but considering the measurement time, the upper limit of the number of divisions is 30. Further, the division is not limited to equal intervals, and the intervals may not be even.

Furthermore, the region division of the surface 50a of the semiconductor substrate 50 may be random. For example, as shown in FIG. 4, six circular regions 54a to 54f of the same size are set on the surface 50a of the semiconductor substrate 50, for example. The position coordinates of each of the six regions 54a to 54f are specified, and a laser beam is irradiated to each region corresponding to the six regions 54a to 54f on the surface 50a of the semiconductor substrate 50, so that the metal set in each region is A seed analysis is performed and defects 51 (see FIG. 1) are analyzed.
Note that when dividing the surface 50a of the semiconductor substrate 50 into regions at random, the sizes of the regions may be the same or different as long as the regions do not overlap.
When setting the region divisions at random, for example, the number of divisions, the size of the regions to be divided, and the arrangement position of the regions are set using pseudo-random numbers. When randomly dividing regions, the condition that the regions do not overlap is added to the setting of the region placement position. As the random region division, Voronoi division can also be used in addition to the above.

(Analysis Department)
The analysis chamber 12d shown in FIG. 1 is provided with an analysis section 30 therein. The analysis unit 30 performs analysis using LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma Mass Spectrometer).
ICP-MS (Inductively Coupled Plasma Mass Spectrometer) uses argon gas plasma at about 10,000° C. generated by inductive coupling to ionize elements in a liquid sample and perform mass spectrometry. In LA-ICP-MS, a laser ablation section (LA section) irradiates a laser beam onto each set area on the surface 50a of a semiconductor substrate 50, and when a defect 51 is irradiated with the laser beam La, the laser beam is emitted. An analysis sample obtained by irradiation with La is introduced into an ICP-MS section (inductively coupled plasma mass spectrometry section) using a carrier gas, and the elements contained in the analysis sample are quantitatively analyzed.

The analysis section 30 includes a stage 32 on which the semiconductor substrate 50 is placed, a container section 33 that stores the semiconductor substrate 50 placed on the stage 32, and a drive section 37 that drives the stage 32. The drive unit 37 is connected to the control unit 42, and the drive unit 37 is controlled by the control unit 42 to move the stage 32 and change the irradiation position of the laser beam La onto the surface 50a of the semiconductor substrate 50.
An analysis unit 36 is connected to the container section 33 via piping 39. The semiconductor substrate 50 is analyzed while being entirely housed in the container section 33. The stage 32 on which the semiconductor substrate 50 is placed is rotatable around the rotation axis _C3 , and can change the position of the semiconductor substrate 50 in the height direction V, and can also be moved in the direction H perpendicular to the height direction V. Can change position.
As described above, the stage 32 is rotated around the rotation axis _C3 by the drive unit 37, and the position of the semiconductor substrate 50 in the height direction V and in the direction H is changed. The drive section 37 is controlled by the control section 42. In order to irradiate the defect 51 on the surface 50a of the semiconductor substrate 50 with the laser beam La, the control section 42 drives the stage 32 using the drive section 37 to change the irradiation position on the surface 50a of the semiconductor substrate 50.

The analysis section 30 includes a light source section 34 that irradiates laser light La onto each of the divided regions on the surface 50a of the semiconductor substrate 50 measured by the alignment measurement section 20. A condensing lens 35 is provided between the light source section 34 and the surface 50a of the semiconductor substrate 50 to focus the laser beam La onto the defect 51 on the surface 50a of the semiconductor substrate 50.
The light source section 34 and the condensing lens 35 are provided outside the container section 33. The container section 33 is provided with a window section (not shown) through which the laser beam La can pass, so that the laser beam La can pass therethrough.
The light source section 34 uses a femtosecond laser, a nanosecond laser, a picosecond laser, an attosecond laser, or the like. As the femtosecond laser, for example, a Ti:Sapphire laser can be used.
Note that the method is not limited to driving the stage 32 to change the irradiation position on the surface 50a of the semiconductor substrate 50, but scanning the laser beam La and changing the irradiation position on the surface 50a of the semiconductor substrate 50 with the laser beam La. A configuration may also be adopted in which the irradiation position is changed.

The analysis section 30 includes a carrier gas supply section 38 that supplies carrier gas into the container section 33 .
The carrier gas supply unit 38 includes a gas supply source (not shown) such as a cylinder in which the carrier gas is stored, a regulator (pressure regulator) connected to the gas supply source, and an adjustment device that controls the supply amount of the carrier gas. and a valve (not shown). For example, the regulator and the regulating valve are connected by a tube, and the regulating valve and the container part 33 are connected by a pipe. For example, helium gas or argon gas is used as the carrier gas.
The analysis section 30 also includes a cleaning gas supply section 40 that supplies cleaning gas into the container section 33 . The cleaning gas supply unit 40 includes a gas supply source (not shown) such as a cylinder in which cleaning gas is stored, a regulator (pressure regulator) connected to the gas supply source, and an adjustment device that controls the supply amount of the cleaning gas. and a valve (not shown). For example, the regulator and the regulating valve are connected by a tube, and the regulating valve and the container part 33 are connected by a pipe. For example, helium gas or argon gas is used as the cleaning gas.

Further, the container portion 33 is provided with an outflow portion 41 that allows the cleaning gas to flow out from inside the container portion 33 to the outside. The outflow portion 41 includes, for example, a pipe and a valve. By opening the valve, the cleaning gas can flow out from inside the container section 33.
A heater (not shown) may be provided in the container portion 33 to perform a flushing process. By heating the inside of the container 33 with a heater while the cleaning gas is supplied into the container 33, foreign matter such as ablated deposits, adsorbed gas, etc. in the container 33 are removed. Thereby, the cleanliness inside the container section 33 can be increased and contamination of the semiconductor substrate 50 can be suppressed. Note that, for example, an infrared lamp or a xenon flash lamp is used as the heater.
In addition to the cleaning gas, a carrier gas can also be used in the flushing process.

<Analysis unit>
The analysis unit 36 utilizes the above-mentioned ICP-MS, and when the defect 51 on the surface 50a of the semiconductor substrate 50 is irradiated with the laser beam La, the analysis sample obtained by the irradiation is collected with a carrier gas. Inductively coupled plasma mass spectrometry. Note that ICP is an abbreviation for inductively coupled plasma, and the analysis unit 36 ionizes the object to be measured using high-temperature plasma maintained by high-frequency electromagnetic induction, and detects the ions with a mass spectrometer to identify atomic species. , and measuring the concentration of the detected atomic species.
For example, a quadrupole mass spectrometer is used as the analysis unit 36. The quadrupole mass spectrometer is arranged in a mass spectrometer 46 (see FIG. 5), which will be described later. In a quadrupole mass spectrometer, the metal species to be measured can be changed by changing the frequency or voltage. For this reason, the frequency or voltage is changed depending on the set metal type to analyze the metal type.
As the analysis unit 36, in addition to the above-mentioned quadrupole mass spectrometer, for example, one having the configuration shown in FIG. 5 can be used. The analysis unit 36 shown in FIG. 5 includes a plasma torch 44 that generates plasma that ionizes an analysis sample introduced together with a carrier gas from a pipe 39, and an ion introduction section located near the tip of the plasma torch 44. It has an analysis section 46.

The plasma torch 44 has, for example, a triple pipe structure, and carrier gas is introduced from a pipe 39. Furthermore, a plasma gas for plasma formation is introduced into the plasma torch 44 . For example, argon gas is used as the plasma gas.
The plasma torch 44 is provided with a high frequency coil (not shown) connected to a high frequency power source (not shown), and this high frequency coil has a power of, for example, 27.12 MHz or 40.68 MHz, about 1 to 2 KW. Plasma is formed inside the plasma torch 44 by applying the high frequency current.

In the mass spectrometer section 46, ions generated by the plasma torch 44 are introduced into the ion lens section 46a and the mass spectrometer section 46b via the ion introduction section. The inside of the ion lens section 46a and the mass spectrometer section 46b are controlled by a vacuum pump (not shown) so that the ion lens section 46a on the plasma torch 44 side is at a low vacuum and the mass spectrometer section 46b is at a high vacuum. The pressure is reduced to

The ion lens section 46a is provided with a plurality of ion lenses 47, for example, three. The ion lens 47 separates ions into the mass spectrometer section 46b.
In the ion lens section 46a of the mass spectrometer 46, the above-mentioned plasma light and ions are separated by an ion lens 47, and only the ions are allowed to pass through.

The mass spectrometer section 46b separates ions according to their mass-to-charge ratios and detects them with the detector 49. The mass spectrometer section 46b includes a reflectron 48 that reflects the ions that have passed through the ion lens section 46a, and a detector 49 that detects the ions. The reflectron 48 is also called an ion mirror, and is a device that uses an electrostatic field to reverse the flying direction of charged particles. By using the reflectron 48, charged particles having the same mass-to-charge ratio and different kinetic energies can be focused on the time axis and made to reach the detector 49 at approximately the same time. Reflectron 48 can compensate for errors and improve mass resolution. As the reflectron 48, a known one used in a time-of-flight mass spectrometer (TOF-MS) can be used.

The detector 49 is not particularly limited as long as it can detect ions and identify elements, and any known detector used in a time-of-flight mass spectrometer (TOF-MS) can be used.
For example, the analysis unit 36 can display the detected element ion signal (not shown) as a chart for each time (not shown). The concentration of the detected element corresponds to the signal intensity.

As shown in FIG. 1, the analyzer 10 has a control section 42. The control unit 42 drives the stage 32 of the analysis unit 30 by the drive unit 37 based on the information on the measurement target area by the alignment measurement unit 20, the information on the divided areas, and the information on the metal type for each area. The irradiation position is changed and a region of the surface 50a of the semiconductor substrate 50 is irradiated with the laser beam La. As a result, a predetermined metal species is measured for each region, and defects 51 on the surface 50a of the semiconductor substrate 50 are analyzed. At this time, the position of the defect 51 is also specified from the irradiation position within the region of the laser beam La, and information about the position of the detected defect 51 and the metal type of the defect 51 within the region is obtained. As a result, position information of the defect 51 in the measurement target region of the semiconductor substrate 50 and information on the metal type of the defect 51 can be obtained, and the distribution of the defect 51 in the measurement target region of the semiconductor substrate 50 can be obtained.

If there are many metal species to be analyzed, the analysis will take time. Furthermore, as the size of the defect to be analyzed becomes smaller, the level of the detection signal obtained also becomes smaller, making it difficult to analyze many types of metals in one analysis. However, in the analyzer 10, the semiconductor substrate is divided into regions and metal species are set for each region, so even if the number of metal species to be analyzed is large, the number of metal species to be measured in each region can be reduced. Therefore, the time required to analyze the defect 51 can be shortened, and as a result, the time required to measure the defect 51 can be shortened. Further, by using laser ablation inductively coupled plasma mass spectrometry using laser light La, it is also possible to analyze small-sized defects 51.
Furthermore, in the analyzer 10, when analyzing a plurality of metal types, one semiconductor substrate 50 can be used, so there is no need to use a plurality of semiconductor substrates. Also from this point of view, the time required for analysis can be reduced.
In addition, the analyzer 10 is configured so that the analyzer 30 can perform inductively coupled plasma mass spectrometry while the entire semiconductor substrate 50 is housed in the container 33, thereby suppressing contamination of the surface 50a of the semiconductor substrate 50. .

In the analyzer 10, the carrier gas and the cleaning gas are supplied through separate systems, but the invention is not limited to this. Since the carrier gas and the cleaning gas have different supply timings, they share one arrangement and are connected to the container section. 33 may be supplied. For example, a configuration may be adopted in which only the carrier gas supply section 38 is provided without providing the cleaning gas supply section 40.
Moreover, it is preferable that the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

When the moisture content of the carrier gas is 0.00001 volume ppm or more and 0.1 volume ppm or less, contamination of the surface 50a of the semiconductor substrate 50 being analyzed in the container section 33 can be reduced. For example, when the carrier gas has a large amount of moisture, impurities are eluted into a small amount of moisture attached to the surface of the carrier gas piping or the inner surface of the container section 33, and these impurities re-deposit on the semiconductor substrate 50, resulting in the number of defects. However, if the moisture content of the carrier gas is within the above range, these can be suppressed.
Further, when the amount of water is small, when the carrier gas passes near the semiconductor substrate 50, the surface 50a of the semiconductor substrate 50 is likely to be charged. As a result, charged particles floating within the container portion 33 are easily attracted to the surface 50a of the semiconductor substrate 50, and particles floating nearby during transport by the transport system are easily attracted to the surface 50a of the semiconductor substrate 50. Further, re-deposition of products resulting from laser ablation is likely to occur, but if the moisture content of the carrier gas is within the above-mentioned range, this can be suppressed.
The amount of water contained in the carrier gas can be measured using an atmospheric pressure ionization mass spectrometer (API-MS). More specifically, the amount of water contained in the carrier gas can be measured using, for example, a product manufactured by Japan API Co., Ltd.
The method for preparing the water content is not particularly limited, but it can be achieved by performing a gas purification step in which water (steam) contained in the raw material gas is removed. In particular, by adjusting the number of times of purification or the filter, the amount of water contained in the carrier gas can be adjusted.
Note that the flow rate of the carrier gas is preferably 1.69×10 ⁻³ to 1.69 Pa·m ³ /sec (1 to 1000 sccm (standard cubic centimeter per minute)).

[First example of analysis method]
The analysis method is a method for analyzing defects located on or inside a semiconductor substrate, and includes a step 1 of setting the number of metal species to be analyzed, a step 2 of dividing the measurement target area of the semiconductor substrate into regions, and a step 2 of dividing the measurement target region of the semiconductor substrate into regions. The method includes a step 3 of assigning a different metal type to each region, and a step 4 of irradiating each region with a laser beam, collecting an analysis sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry. Note that the meaning of "assigning different metal types" in step 3 of allocating different metal types to each of the divided regions is as described above.
In the step 3 of assigning different metal types, completely different metal types may be assigned to each area so that the metal types do not overlap in each area, and the metal types may be different from each other except that the metal types in each area completely match. Some parts may be allocated redundantly.
Furthermore, in Step 3 of allocating different metal types, when allocating different metal types, it is not limited to allocating the same number of metal types to each area, and the number of metal types may be different in each area. .
The analysis method will be specifically explained below.
FIG. 6 is a schematic cross-sectional view illustrating a first example of the analysis method according to the embodiment of the present invention. In FIG. 6, the same components as those of the analyzer 10 shown in FIG. 1 are designated by the same reference numerals, and detailed explanation thereof will be omitted.

In the analysis method, for example, a storage container 13 (see FIG. 1) containing a plurality of semiconductor substrates 50 is connected to an introduction section 12g on the side surface of the first transfer chamber 12a of the analysis apparatus 10 shown in FIG. The lid of the storage container 13 is opened and the semiconductor substrate 50 is taken out from the storage container 13.
Next, the semiconductor substrate 50 is taken out from inside the storage container 13 using the transfer device 14 of the first transfer chamber 12a, and the semiconductor substrate 50 is transferred to the stage 22 of the measurement chamber 12b. By the process of transporting the semiconductor substrate 50 from inside the storage container 13 to the stage 22 of the measurement chamber 12b, contamination of the semiconductor substrate 50 is suppressed even if the semiconductor substrate 50 is transported from outside the analysis apparatus 10.

Next, in a state where contamination of the semiconductor substrate 50 is suppressed, the alignment measuring section 20 irradiates the light Ls from the light source 23 in the measurement chamber 12b, the semiconductor substrate 50 is imaged by the imaging section 24, and the semiconductor substrate 50 is The contour information of the surface 50a of 50 is obtained. Information on the measurement target area of the semiconductor substrate 50 can be obtained from this contour information as described above. Furthermore, as described above, information on the center position of the semiconductor substrate 50 can also be obtained.
In addition, in the alignment measurement section 20, when the semiconductor substrate 50 has a notch, orientation flat, or alignment mark as described above, the notch, orientation flat, or alignment mark is imaged, and the calculation section 27 determines the notch, orientation flat, or alignment mark. Information on the position of the mark can also be obtained. Furthermore, the calculation unit 27 also obtains information on the center position of the semiconductor substrate 50.
As described above, information on the outline of the surface 50a of the semiconductor substrate 50 and information on the measurement target area, information on the position of the notch, orientation flat or alignment mark, and information on the center position of the semiconductor substrate 50 are stored in the storage unit 26. Ru.

Next, the semiconductor substrate 50 is transported from the measurement chamber 12b to the analysis chamber 12d by the transport device 16 of the second transport chamber 12c shown in FIG.
Here, the setting unit 28 sets the number of metal species to be analyzed, divides the measurement target region of the semiconductor substrate into regions, and assigns a different metal species to each divided region. At this time, the two-dimensional positional coordinates of each region set on the surface 50a of the semiconductor substrate 50 have been specified.
Based on the two-dimensional positional coordinates of each region, the calculation unit 27 calculates the range to be irradiated with the laser beam La and the positional coordinates of the range for each region of the semiconductor substrate 50 based on the contour information. The calculation unit 27 further determines the range to be irradiated with the laser beam La and the metal type to be measured in the range to be irradiated with the laser beam La, and obtains combination data of the range to be irradiated with the laser beam La and the metal type to be measured. create. The combination data is stored in the storage unit 26.
Note that the information set in the setting section 28 is input via the input section 29. Further, for example, the step of setting the number of metal types to be analyzed in the setting unit 28 may include the step of setting the metal types to be analyzed. The metal species to be analyzed are, for example, metal species such as Fe, Al, Cu, and Ni, similar to the information on the metal species to be analyzed described above.
Note that once the metal species to be analyzed is set, the number of metal species to be analyzed is determined. On the other hand, it is also possible to set the metal types to be analyzed after determining the number of metal types to be analyzed.

Next, in the analysis chamber 12d, the analysis section 30 performs analysis based on the above-mentioned combination data. As shown in FIG. 6, the analysis is performed with the entire semiconductor substrate 50 housed in the container section 33 and with a carrier gas (not shown) being supplied into the container section 33 from the carrier gas supply section 38. . During the analysis, the stage 32 of the analysis section 30 is driven to change the irradiation position of the laser beam La based on the above combination data, and the region of the surface 50a of the semiconductor substrate 50 is irradiated with the laser beam La.
At this time, as shown in FIG. 6, when the defect 51 on the surface 50a of the semiconductor substrate 50 is irradiated with the laser beam La, the analysis sample 51a obtained by irradiating the defect 51 with the laser beam La is transferred to the carrier gas ( (not shown) via a pipe 39 to an analysis unit 36. The analysis sample 51a originating from the defect 51, which has been moved by the carrier gas, is subjected to inductively coupled plasma mass spectrometry in the analysis unit 36 to identify the element of the defect 51. The analysis unit 36 measures metal species set for each region. Therefore, metal types other than those set for each region are not measured.
Also in the analysis method, since the semiconductor substrate is divided into regions and the metal type is set for each region, the time required to analyze the defect 51 can be shortened, and as a result, the time required to measure the defect can be shortened. Further, by using laser ablation inductively coupled plasma mass spectrometry using laser light La, it is possible to analyze small-sized defects 51.

The analysis method preferably includes a step of cleaning the inside of the container part 33 using a cleaning gas before the analysis step. Specifically, in the cleaning step, before transporting the semiconductor substrate 50 into the container section 33, a cleaning gas is supplied into the container section 33, the inside of the container section 33 is heated using a heater, and a flushing process is performed. This is the process of implementing. The cleaning step removes foreign matter such as ablated deposits, adsorbed gas, etc. in the container portion 33 .

Here, it is preferable that the setting unit 28 sets the number of hit metal types for one region of the semiconductor substrate to 4 to 10. If the number of metal species per region of the semiconductor substrate is 4 to 10, the measurement time can be shortened.
Further, the setting unit 28 may set the winning metal type for one region of the semiconductor substrate to 2 or 3, or may set the winning metal type for one region of the semiconductor substrate to 1. If the number of metal species allocated to one region is small, it is necessary to increase the number of region divisions when there are many metal species to be measured. In this case, the number of areas to be measured increases. For this reason, it is preferable to appropriately determine the number of metal species to be assigned to one region of the semiconductor substrate 50 and the number of region divisions, depending on the number of metal species to be measured.
Note that in the analysis method as well, it is preferable to set the number of metal types per region of the semiconductor substrate to 4 to 10, similarly to the analysis apparatus 10. Furthermore, the number of contact metal types for one region of the semiconductor substrate may be set to two or three, or the number of contact metal types for one region of the semiconductor substrate may be set to one.

In the analysis device 10 and analysis method, when the semiconductor substrate 50 itself is measured without applying a chemical or the like, defects on the surface 50a or inside the semiconductor substrate 50 are analyzed.
Here, the inside of the semiconductor substrate 50 is a range up to 100 μm from the surface 50a of the semiconductor substrate 50.
In addition, in the analyzer 10 and the analysis method, when the surface 50a of the semiconductor substrate 50 is analyzed with a chemical solution etc. applied to the surface 50a of the semiconductor substrate 50, or in a state where the chemical solution is dried after being applied, the applied chemical solution is Defects are also analyzed.

Here, FIG. 7 is a flowchart showing a first example of the analysis method according to the embodiment of the present invention. FIG. 7 describes an example in which a chemical solution is applied to the surface of a semiconductor substrate.
The analysis method described below is carried out using the analysis apparatus 10 shown in FIG. 1 as described above.
First, a chemical solution to be analyzed is prepared (step S10).
Next, a chemical solution is applied onto a semiconductor substrate (not shown) (step S12).
Step S12 is an example of a step of bringing the semiconductor substrate into contact with the chemical liquid, and the contact with the chemical liquid is not particularly limited. Furthermore, although there are no particular limitations on how to apply the chemical solution to the semiconductor substrate, for example, a coater-developer may be used.
Next, as described above, the alignment measuring section 20 obtains contour information of the semiconductor substrate (step S14). As described above, information on the measurement target area is obtained from the contour information.
Next, inductively coupled plasma mass spectrometry is performed (step 4, step S16), but in order to implement step S16, the following setting step (step S15) needs to be performed.

In the setting step (step S15), a metal type is assigned to each divided region.
Specifically, in step S15, first, the number of metal species to be analyzed is set (process 1, step S15a). The number of metal species to be set is, for example, 10. The method may also include a step of setting metal types to be analyzed among the set 10 metal types. In this case, the metal type to be analyzed is set for the set 10 metal types. The metal species to be analyzed is appropriately determined depending on the application to be analyzed, and Fe, Al, Cu, Ni, etc. are selected. In step S15a, after determining the number of metal types to be analyzed as described above, the metal types to be analyzed are set, but the present invention is not limited to this. By setting the metal species to be analyzed, the number of metal species to be analyzed may be set.
Next, the measurement target region of the semiconductor substrate is divided into regions (Step 2, Step S15b). In step S15b, a measurement area on the semiconductor substrate is set by area division. For example, the number of regions obtained by region division is set in advance. Alternatively, the number of metal species to be analyzed and the number of regions may be set in advance, and the number of regions may be determined based on these. If the number of metal species is 10 as described above, the number of regions is, for example, 2. For region division, for example, any of the forms shown in FIGS. 2 to 4 described above is used. When the number of regions is two, for example, the circular semiconductor substrate 50 is divided into semicircular regions by a line passing through the center and corresponding to the diameter. Based on the information on each region of the semicircular region and the information on the measurement target region of the semiconductor substrate, the range to be irradiated with laser light and the position coordinates of the range are calculated on the semiconductor substrate 50.

Next, a different metal type is assigned to each divided region (Step 3, Step S15c). In step S15c, for example, five metal types out of ten metal types are set in each of the two areas. In this case, different metal types are set in each of the two regions, and there is no overlapping metal type in each region. That is, each region is assigned a completely different metal type.
As a result, the range to be irradiated with the laser beam La and the metal type to be measured are determined, and the combination data of the range to be irradiated with the laser beam La and the metal type to be measured is obtained. The combination data is stored in the storage unit 26.
In step S15c (step 3) of allocating different metal types to each of the divided regions described above, different metal types are assigned to each of the divided regions, but the metal types are not overlapped in each region. A metal type may be assigned to the region, or a portion of the metal species may be assigned redundantly, except that the metal species completely match in each region.
When metal types overlap, instead of setting 5 metal types out of 10 metal types in each area, for example, overlap 2 out of 10 metal types in each area, and set 6 metal types. The metal type may be set for each type. Note that the number of overlapping metal species is not particularly limited, but if there are many overlapping metal species, the number of metal species per area increases, so it should be 35% or less of the number of metal species to be analyzed. is preferred.

In step S15, as described above, information on the metal species assigned to each divided region is obtained in the order of steps S15a (step 1) to S15c (step 3), that is, the above-mentioned combination data. , the order of steps S15a to S15c is not limited as long as the combination data can be obtained. For example, the order may be step S15b (process 2), step S15a (process 1), and step S15c (process 3), or the order of step S15b (process 2), step S15c (process 3), and step S15a (process 1). good.
In addition, without obtaining combination data using steps S15a (step 1) to S15c (step 3) described above, it is possible to determine the number of metal species to be analyzed, the region division of the measurement target region, and the division of each region. Setting information including the assigned metal species may be used for inductively coupled plasma mass spectrometry (Step 4, Step S16). Note that the setting information may include information on the metal species to be analyzed as described above.
Note that the metal type assigned to each divided area in the setting information is similar to step S15c (step 3) in which a different metal type is assigned to each divided area described above. In this example, different metal types are set for each area, but you can also assign metal types so that the metal types do not overlap in each area. Duplicate allocations may be made.
Further, the contour information is not limited to measurement, and a previously measured value of the contour shape of the semiconductor substrate may be used.

Next, the stage 32 is driven and the position of the stage 32 is adjusted based on the information on the metal type assigned to each divided region, that is, the above-mentioned combination data. A laser beam is irradiated, and an analysis sample obtained by the irradiation is collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry (Step 4, Step S16). The metal species set for each region is analyzed by inductively coupled plasma mass spectrometry in step S16 (process 4), and the metal element of the defect is identified. The size of minute defects is also determined. Inductively coupled plasma mass spectrometry provides mass spectrometry data for defects in chemical solutions. The mass spectrometry data of the chemical solution includes information on the element of the defect identified by inductively coupled plasma mass spectrometry and information on the size of the defect. In this way, the chemical liquid can be tested, and the method for testing the chemical liquid allows analysis of minute foreign substances in the chemical liquid.

Although FIG. 7 describes an example in which a chemical solution is applied to the surface of the semiconductor substrate, if the chemical solution is not applied, defects on the surface or inside of the semiconductor substrate will be analyzed as described above. When analyzing defects on the surface or inside of a semiconductor substrate, step S10 and step S12, which will be described later, are skipped.
When defects on the surface or inside of a semiconductor substrate are analyzed, mass spectrometry data of the defects on the surface or inside of the semiconductor substrate can be obtained by inductively coupled plasma mass spectrometry. This mass spectrometry data includes information on the element of the defect identified by inductively coupled plasma mass spectrometry and information on the size of the defect.

With the analysis device and analysis method, it is possible to identify the element of a minute defect, thereby making it possible to measure minute foreign matter and even inspecting a chemical solution.
For inductively coupled plasma mass spectrometry, a chemical solution is applied to a semiconductor substrate, and minute foreign particles in the chemical solution can be analyzed. In inductively coupled plasma mass spectrometry, the chemical solution may be on the semiconductor substrate, and after the chemical solution is applied to the semiconductor substrate, the solvent contained in the chemical solution is volatilized or evaporated so that the solvent contained in the chemical solution is not on the semiconductor substrate. Inductively coupled plasma mass spectrometry may be performed in this state.

In addition, in the analyzer 10, the contour of the surface 50a of the semiconductor substrate 50 is measured using another device different from the analyzer 10, for example, the contour measuring device 70 (see FIG. 1). Contour information on the surface 50a and information on the measurement target area can be used. If the semiconductor substrate 50 has a notch, orientation flat, or alignment mark, this contour information includes information on the position of the notch, orientation flat, or alignment mark. As described above, information on the center position of the semiconductor substrate 50 can also be obtained from the contour information.
The contour information and measurement target area information acquired by the contour measuring device 70 are supplied to the storage unit 26 . Furthermore, the semiconductor substrate 50 whose contour information has been acquired by the contour measuring device 70 is stored in, for example, a storage container 13 and transported to the analysis device 10 . The semiconductor substrate 50 is transported to the analysis chamber 12d via the first transport chamber 12a, the measurement chamber 12b, and the second transport chamber 12c.
The calculation unit 27 determines the range to be irradiated with the laser beam La and the type of metal to be measured in the range to be irradiated with the laser beam La for each area of the semiconductor substrate 50 based on the information of the measurement target area, and determines the type of metal to be measured in the range to be irradiated with the laser beam La. Obtain data on the combination of the irradiation range and the metal species to be measured. The combination data is stored in the storage unit 26.
Based on the combination data, the semiconductor substrate 50 is moved using the stage 32, and each region of the surface 50a of the semiconductor substrate 50 is irradiated with laser light La. An analysis sample 51a (see FIG. 6) obtained by irradiating the defect 51 with the laser beam La is moved to the analysis unit 36 by a carrier gas. The analysis sample 51a originating from the defect 51, which has been moved by the carrier gas, is subjected to inductively coupled plasma mass spectrometry in the analysis unit 36. At this time, if the element of the defect 51 is the set metal type, it is specified, but if it is not the set metal type, the element is not specified.

When analyzing the defect 51 using the contour information measured by the contour measuring device 70 (see FIG. 1) and the information of the measurement target area as described above, the measurement by the alignment measuring section 20 becomes unnecessary. It goes without saying that the analyzer 10 may have a configuration in which the contour measuring device 70 shown in FIG. 1 is not provided.
Note that the contour information supplied to the storage unit 26 is not particularly limited to that measured by the contour measuring device 70 (see FIG. 1). The contour measuring device 70 may include, for example, a storage section (not shown) that stores contour information of the semiconductor substrate. Further, the contour measuring device 70 may have the same configuration as the alignment measuring section 20 (see FIG. 1). Therefore, the contour measuring device 70 may have a configuration including, for example, a light source 23 that makes light Ls incident on the surface 50a of the semiconductor substrate 50, and an imaging section 24 that images the surface 50a of the semiconductor substrate 50.
Moreover, when using the above-mentioned setting information, the setting unit 28 of the analyzer 10 is not necessarily required.

[Second example of analyzer]
FIG. 8 is a schematic diagram showing a second example of the analyzer according to the embodiment of the present invention. In FIG. 8, the same components as those of the analyzer 10 shown in FIG. 1 are given the same reference numerals, and detailed explanation thereof will be omitted.
The analyzer 10a shown in FIG. 8 differs from the analyzer 10 shown in FIG. The other configuration is the same as that of the analyzer 10 shown in FIG.

In the analysis device 10a, acquisition and analysis of contour information are performed with the entire semiconductor substrate 50 housed in the container section 33.
In the analysis section 30, the light source section 34 is arranged such that the optical axis of the laser beam La is inclined with respect to the surface 50a of the semiconductor substrate 50.
In the analyzer 10a, by providing the alignment measurement section 20 and the analysis section 30 in one processing chamber 12e, the analyzer 10a can be made smaller than the analyzer 10 shown in FIG.
Further, by adopting a configuration in which the alignment measuring section 20 can measure surface defects and the analyzing section 30 can perform inductively coupled plasma mass spectrometry while the entire semiconductor substrate 50 is housed in the container section 33, the semiconductor substrate 50 can be transported. Therefore, contamination of the surface 50a of the semiconductor substrate 50 can be further suppressed. Thereby, the accuracy of measuring defects on the surface 50a of the semiconductor substrate 50 can be improved, and furthermore, the contamination in the processing chamber 12e of the analysis device 10a can be suppressed.
As mentioned above, when using contour information measured by a device other than the

analyzers

10, 10a, for example, the contour measuring device 70, the alignment measuring section is not necessarily required in the

analyzers

10, 10a, and the analyzer A configuration without an alignment measuring section may also be used. In this case, the

analyzers

10 and 10a have only the analyzer 30 (see FIG. 1). In this case, the

analysis devices

10, 10a and the contour measuring device 70 are separate devices and are not integrated.

[Semiconductor substrate]
The semiconductor substrate is not particularly limited, and various semiconductor substrates such as a silicon (Si) substrate, a sapphire substrate, a SiC substrate, a GaP substrate, a GaAs substrate, an InP substrate, or a GaN substrate can be used. Silicon semiconductor substrates are often used as semiconductor substrates.
Further, the size of the semiconductor substrate is not particularly limited, but is appropriately determined depending on the specifications of the apparatus for performing inductively coupled plasma mass spectrometry. Furthermore, when analyzing a chemical solution, the size of the semiconductor substrate is appropriately determined in consideration of the specifications of a coating device that applies the chemical solution to the semiconductor substrate.

[How to manage chemical solutions]
The above-mentioned analysis method can be used as a method for managing chemical solutions. The results of inductively coupled plasma mass spectrometry are used in the management of chemical solutions.
Further, for example, in a chemical solution management method, an allowable range of mass spectrometry data of defects with respect to preset reference data is set in advance. Defects in the chemical liquid are measured using the above-described chemical liquid management method, and mass spectrometry data of the defects is obtained. The measured mass spectrometry data of defects in the chemical solution is compared with preset reference data to determine whether the mass spectrometry data is within an acceptable range. Those whose mass spectrometry data is within the allowable range are considered to be passed and manufactured as products. On the other hand, if the mass spectrometry data is outside the acceptable range, it is rejected and the product is not manufactured. For example, when the data acquisition interval is 1 msec, the allowable range of standard data for chemical solutions is as follows: If the data acquisition interval is 1 msec, the number of Fe (mass number 56) peaks of 1 x 10 ⁷ cps (count per second) or more is 100/(12 inch wafer area). (706.5 cm ² )) or less. The allowable range of the standard data of this chemical solution is used as the determination standard.
FIG. 9 is a flowchart illustrating an example of the chemical solution management method according to the embodiment of the present invention. In addition, in the method for managing a chemical solution, detailed explanations of the same steps as those in the above-mentioned analysis method will be omitted.
The chemical solution management method shown in FIG. 9 is different from the above-mentioned analysis method in that the chemical solution to be managed is prepared (step S20), and the mass spectrometry data obtained by inductively coupled plasma mass spectrometry (step S26) is This is a method for testing chemical solutions, except that it includes a step of determining whether or not it is within the allowable range (step S28), and that it is divided into pass (step S29) or fail (step S30) based on the above-mentioned determination step. It has similar steps.
First, a chemical solution to be managed is prepared (step S20). A chemical solution is applied onto the surface of the semiconductor substrate (step S22). Next, contour information of the semiconductor substrate is acquired (step S24).
Note that steps S20, S22, and S24 described above are the same steps as steps S10, S12, and S14 shown in FIG. 7 described above, so detailed explanation thereof will be omitted.
Further, in the setting step (step S25), a metal type is assigned to each divided region and set in the setting section 28. The setting step (step S25) in the chemical solution management method is the same step as the above-mentioned setting step (step S15), so a detailed explanation thereof will be omitted. Steps S25a, S25b, and S25c are the same steps as steps S15a, S15b, and S15c described above. For this reason, when a metal type is assigned to each of the above-mentioned area-divided areas, the metal type may be assigned so that the metal types do not overlap in each area, similarly to step S15c. A portion of the metal species may be assigned redundantly, except that they are a perfect match.
In the setting step (step S25), combination data is obtained in the same way as in the above-mentioned setting step (step S15).
Next, inductively coupled plasma mass spectrometry (step S26) is performed. This inductively coupled plasma mass spectrometry (step S26) is also the same process as the above-described inductively coupled plasma mass spectrometry (step S16), so detailed explanation thereof will be omitted. In inductively coupled plasma mass spectrometry (step S26), combined data is used in the same way as in the above analysis method.
Next, the mass spectrometry data obtained by inductively coupled plasma mass spectrometry (step S26) is compared with reference data to determine whether it is within an allowable range (step S28). Step S28 is also referred to as a determination step.

In the chemical solution management method, standard data is set in advance for the mass spectrometry data of the drug solution, and an allowable range is set. The tolerance range for the mass spectrometry data of the chemical solution with respect to the standard data is set, for example, based on the drug solution of the previous manufacturing lot of the target drug solution, but is not limited to this, and the tolerance range can be set based on the target value or the target value. It may be a set value or an average value of multiple production lots. The allowable range of the mass spectrometry data of the chemical solution with respect to the standard data is as described above.
Step S28 compares the mass spectrometry data obtained in step S26 described above with reference data. In step S28, for example, if the measured mass spectrometry data of the chemical liquid is within an acceptable range, the chemical liquid is determined to be an acceptable product (step S29).
On the other hand, if the mass spectrometry data of the chemical liquid is outside the allowable range in step S28, the chemical liquid is determined to be a rejected product (step S30). In this way, the quality of the chemical solution can be controlled based on defects in the drug solution. With the chemical solution management method, it is possible to control the quality of the chemical solution even when the amount of minute foreign matter contained in the drug solution is minute.

Similar to the above-mentioned analysis method, the number of metal species to be analyzed, the region division of the measurement target region, and the metals assigned to each divided region can be determined without obtaining combination data using the above-mentioned setting step 25. The setting information including the species may be used for inductively coupled plasma mass spectrometry (step S26).
Note that the method for managing a chemical solution can be applied to a method for managing a resist composition by using a resist composition instead of the above-mentioned chemical solution. In the case of a resist composition, defects in a coating film of the resist composition formed on the surface of a semiconductor substrate are analyzed.

[Management method of resist composition]
The above analysis method can be used as a method for managing resist compositions. The results of inductively coupled plasma mass spectrometry are used in a resist composition management method. In the resist composition management method, defects in a coating film of a resist composition formed on the surface of a semiconductor substrate are analyzed.
Further, for example, in a resist composition management method, an allowable range is set in advance for mass spectrometry data of defects with respect to preset reference data. Defects in the resist composition are measured using the above-described resist composition management method to obtain mass spectrometry data of the defects. The measured mass spectrometry data of defects in the chemical solution is compared with preset reference data to determine whether the mass spectrometry data is within an acceptable range. Those whose mass spectrometry data is within the allowable range are considered to be passed and manufactured as products. On the other hand, if the mass spectrometry data is outside the acceptable range, it is rejected and the product is not manufactured. For example, when the data acquisition interval is 1 msec, the allowable range of the standard data of the resist composition is 100 peaks of Fe (mass number 56) of 1×10 ⁷ cps (count per second) or more/(12 inches). wafer area (706.5 cm ² )). The allowable range of the standard data of this chemical solution is used as the determination standard.

FIG. 10 is a flowchart showing an example of a resist composition management method according to an embodiment of the present invention. In addition, in the resist composition management method, detailed explanations of the same steps as the above-mentioned chemical solution management method will be omitted.
The resist composition management method shown in FIG. 10 differs from the chemical solution management method in that a resist composition to be managed is prepared (step S40). Another difference is that the resist composition is applied to the semiconductor substrate (step S42), and a film is formed after the application, thereby forming a coating film of the resist composition on the semiconductor substrate. Other than these, the resist composition management method has the same steps as the chemical solution management method.
Application of the resist composition to the semiconductor substrate is not particularly limited, and for example, a coater-developer may be used.
The step of acquiring the contour information of the semiconductor substrate (step S44) is the same step as step S24 shown in FIG. 9 described above, so a detailed explanation thereof will be omitted.
Further, in the setting step (step S45), a metal type is assigned to each divided region and set in the setting section 28. The setting step (step S45) in the resist composition management method is the same step as the above-mentioned setting step (step S25), so detailed explanation thereof will be omitted. Steps S45a, S45b, and S45c are the same steps as steps S25a, S25b, and S25c described above. Therefore, in assigning a metal type to each of the divided regions described above, in step S25c, similarly to step S15c, metal types may be assigned so that the metal types do not overlap in each region. Unless the metal types completely match in each region, some of the metal types may be assigned redundantly.
In the setting step (step S45), combination data is obtained in the same manner as in the above-mentioned setting step (step S25).
Next, inductively coupled plasma mass spectrometry (step S46) is performed. This inductively coupled plasma mass spectrometry (step S46) is also the same process as the above-described inductively coupled plasma mass spectrometry (step S26), so detailed explanation thereof will be omitted. In inductively coupled plasma mass spectrometry (step S26), combined data is used in the same way as the above-mentioned chemical solution management method and analysis method.
Next, the mass spectrometry data obtained by inductively coupled plasma mass spectrometry (step S46) is compared with reference data to determine whether it is within an allowable range (step S48). Step S48 is also referred to as a determination step. Step S48 is also a step similar to step S28 of the above-described chemical solution management method.

In the resist composition management method as well, similar to the chemical solution management method, reference data is set in advance and an allowable range is set for mass spectrometry data of a coating film of the resist composition. The tolerance range for the mass spectrometry data of the coating film of the resist composition with respect to the standard data is set, for example, based on the resist composition of the previous production lot of the target resist composition, but is not limited to this. Instead, the tolerance range may be a target value, a set value, or an average value of multiple manufacturing lots. The allowable range of the mass spectrometry data of the coating film of the resist composition with respect to the standard data is as described above.
Step S48 compares the mass spectrometry data obtained in step S46 described above with reference data. In step S48, for example, if the measured mass spectrometry data of the coating film of the resist composition is within an acceptable range, the resist composition is determined to be an acceptable product (step S49).
On the other hand, if the mass spectrometry data of the resist composition is outside the allowable range in step S48, the resist composition is determined to be a rejected product (step S50). In this way, the quality of the resist composition can be controlled based on defects in the coating film of the resist composition. The resist composition control method allows quality control of the resist composition even when a minute amount of foreign matter is contained in the coating film of the resist composition.

Similar to the above-mentioned analysis method, the number of metal species to be analyzed, the region division of the measurement target region, and each region divided into Setting information including the assigned metal species may be used for inductively coupled plasma mass spectrometry (step S46).

In addition to the above-mentioned resist composition management method, the chemical solution management method can also be applied to the management of resist composition raw materials, slurry (polishing liquid), developer, cleaning liquid, and their raw materials.

[Medicinal solution]
The chemical solution contains an organic solvent as a main component.
In this specification, the term "organic solvent" refers to a liquid organic compound contained in an amount exceeding 10,000 ppm by mass per component based on the total mass of the above-mentioned chemical solution. That is, in this specification, a liquid organic compound contained in an amount exceeding 10,000 mass ppm with respect to the total mass of the above-mentioned chemical solution corresponds to an organic solvent.
Moreover, in this specification, liquid means being liquid at 25° C. and under atmospheric pressure.

The phrase "organic solvent is the main component in the drug solution" means that the content of the organic solvent in the drug solution is 98.0% by mass or more based on the total mass of the drug solution, and more than 99.0% by mass. is preferable, more preferably 99.90% by mass or more, and even more preferably more than 99.95% by mass. The upper limit is less than 100% by mass.
One type of organic solvent may be used alone or two or more types may be used. When using two or more types of organic solvents, the total content is preferably within the above range.

The type of organic solvent is not particularly limited, and any known organic solvent can be used. Examples of organic solvents include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), and monoketone compounds that may have a ring. (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkoxy alkyl acetate, alkyl pyruvate, dialkyl sulfoxide, cyclic sulfone, dialkyl ether, monohydric alcohol, glycol, acetic alkyl ester, and N-alkylpyrrolidone. .

Examples of organic solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), 4-methyl-2 -Pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N- One or more selected from the group consisting of methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, and 2-heptanone is preferred.
Examples of using two or more types of organic solvents include a combination of PGMEA and PGME, and a combination of PGMEA and PC.
Note that the type and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.

The chemical solution may contain impurities in addition to the organic solvent.
Examples of impurities include metal impurities.
The term "metal impurities" refers to metal ions and metal impurities contained in a chemical solution as a solid (elementary metal, particulate metal-containing compound, etc.).
The types of metal elements contained in the metal impurities are not particularly limited, and examples include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), and Mn (manganese). ), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium).
Metal impurities may be components that are unavoidably included in each component (raw material) contained in the drug solution, components that are unavoidably included during the manufacturing, storage, and/or transportation of the drug solution, or components that are intentionally included in the drug solution. May be added to.

The chemical solution may contain water. The type of water is not particularly limited, and for example, distilled water, ion exchange water, and pure water can be used.
Water may be added to the chemical solution, or may be unavoidably mixed into the drug solution during the process of manufacturing the drug solution. Examples of cases where water is unavoidably mixed in the manufacturing process of a chemical solution include cases where water is included in raw materials (e.g., organic solvents) used in the manufacturing process of a chemical solution, and cases where water is mixed in the manufacturing process of a chemical solution (e.g., due to contamination). ) etc.

The content of water in the chemical solution is not particularly limited, but in general, it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even less than 0.5% by mass, based on the total mass of the chemical solution. preferable.
When the water content in the chemical solution is 1.0% by mass or less, the manufacturing yield of semiconductor chips is better.
Note that the lower limit is not particularly limited, but is often about 0.01% by mass. In production, it is difficult to reduce the water content to below the above-mentioned value.

The method for preparing the above-mentioned chemical solution is not particularly limited, and examples thereof include methods such as procuring an organic solvent by purchasing or the like, and obtaining an organic solvent by reacting raw materials. Note that it is preferable to prepare a chemical solution containing a small amount of the impurities described above (for example, one containing an organic solvent of 99% by mass or more). Examples of commercially available organic solvents include those called "high purity grade products."
Note that, if necessary, the chemical solution may be subjected to purification treatment.
Examples of purification methods include distillation and filtration.

The chemical solution contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total content of the metal elements is preferably 10 mass ppb or less based on the total mass of the chemical solution.
If it exceeds 10 mass ppb, the index of mass ppb measured by a surface inspection device (SurfScan SP5; manufactured by KLA Corporation), ICP-MS, etc. will not correlate and the coefficient of determination will become small.
The contents of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn in the chemical solution were determined by ICP-MS (trade name, manufactured by PerkinElmer) using NexION350 (trade name, PerkinElmer). It can be measured using the inductively coupled plasma mass spectrometry method. Specific measurement conditions by the ICP-MS method are as follows. Note that the detected amount is measured based on the peak intensity with respect to a standard solution with a known concentration, and is converted into the mass of the metal component to calculate the content of the metal component (total metal content) in the processing solution used for measurement.
The content of metal components was measured by the usual ICP-MS method. Specifically, software for ICP-MS is used as software for analyzing metal components.

The above-mentioned measurement of 0.01 mass ppq will be explained.
First, 1 mL of a chemical solution is applied as a droplet onto a silicon wafer with a diameter of about 300 mm (12 inches). Then, dry without rotating. After measuring the defect position of the silicon wafer using a surface inspection device (SurfScan SP7; manufactured by KLA Corporation), the coordinate file acquired by the surface inspection device (SurfScan SP7) is measured using a FIB-SEM (HELIOS G4-EXL manufactured by Thermo Fisher). Based on the base, cut out a cross section near the defect site.
FIB (Focused Ion Beam)-SEM (Scanning Electron Microscope) or TEM (Transmission Electron Microscope) performs cross-sectional etching while EDX acquires three-dimensional shape information and elemental information. Perform these steps for all defects.
For example, if one spherical particle of Fe13.5 nm (the limit of the surface inspection device (SurfScan SP7)) is found in 1 mL (density 1 g/cm ³ ) of chemical solution, in principle This means that 0.01 mass ppq can be measured.

[Applications of chemical solution]
A chemical solution containing an organic solvent as a main component is used, for example, in a method for manufacturing semiconductor devices and a method for cleaning semiconductor manufacturing equipment. Specifically, the chemical solution is used, for example, as a developer, a rinse solution, and a pre-wet solution. In addition to this, the chemical liquid is used as an edge rinse liquid, a back rinse liquid, a resist stripping liquid, and a thinner for dilution.
Pre-wet liquid is supplied onto the semiconductor substrate before forming the resist film, and is used to make it easier to spread the resist liquid over the semiconductor substrate and to form a uniform resist film with a smaller amount of resist liquid supplied. It is used for.
The above-mentioned edge rinsing liquid refers to a rinsing liquid that is supplied to the peripheral edge of a semiconductor substrate and used to remove a resist film on the peripheral edge of the semiconductor substrate.
For example, butyl acetate (nBA) is used as the developer. Butyl acetate (nBA) can be used not only as a developer but also as a cleaning solution for piping, a cleaning solution for semiconductor wafers, and the like.
Furthermore, 4-methyl-2-pentanol (MIBC) is used as the rinse liquid. Propylene glycol monomethyl ether acetate (PGMEA) and isopropanol (IPA) are used as the cleaning liquid. Cyclohexanone (CHN) is used as the pre-wet liquid.

[Resist composition]
The type of resist composition is not particularly limited, and any known resist composition can be used.
For example, as resist compositions, resins (hereinafter also simply referred to as "acid-decomposable resins") having groups that generate polar groups under the action of acids (hereinafter also simply referred to as "acid-decomposable groups"), photoacid A resist composition (hereinafter also referred to as "first resist composition") containing a generator and a solvent can be used.
The acid-decomposable group preferably has a structure in which a polar group is protected with a leaving group that is eliminated by the action of an acid. That is, the acid-decomposable resin has a repeating unit having an acid-decomposable group. A resin having this repeating unit has increased polarity due to the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.
The polar group is preferably an alkali-soluble group, such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Examples include acidic groups such as methylene group and tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.

The acid-decomposable resin contains repeating units other than repeating units having an acid-decomposable group (for example, repeating units having an acid group, lactone groups, sultone groups, or repeating units having a carbonate group, fluorine atoms or iodine atoms). (e.g., a repeating unit having
As the acid-decomposable resin, known acid-decomposable resins can be used.

The photoacid generator is not particularly limited as long as it is a known one, but it can generate organic acids such as sulfonic acid, bis(alkylsulfonyl)imide, and Compounds that generate at least one of tris(alkylsulfonyl)methides are preferred.

Examples of solvents include water and organic solvents. The type of organic solvent is not particularly limited, and examples include alcohol solvents, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents.

The first resist composition may contain materials other than the acid-decomposable resin, the photoacid generator, and the solvent.
For example, the first resist composition may include an acid diffusion control agent. The acid diffusion control agent is a basic compound and a compound that has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation, and the proton acceptor property decreases or disappears, or the proton acceptor property is reduced. Examples include compounds that generate a compound that changes from acidic to acidic.
The first resist composition also includes a hydrophobic resin, a surfactant, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer. It may also contain selected compounds.

The resist composition includes a crosslinking agent having a crosslinking group, a compound having a reactive group that reacts with the crosslinking group, and a solvent (hereinafter also referred to as "second resist composition"). It may be.
The combination of a crosslinkable group and a reactive group is not particularly limited, and known combinations may be employed.
Note that the crosslinkable group or the reactive group may be protected with a protecting group. For example, the second resist composition further contains a photoacid generator, and the protecting group is protected by the acid generated from the photoacid generator. It may also be in a form where it is desorbed. Alternatively, a crosslinked structure may be formed by causing a condensation reaction between the crosslinking agent and the resin due to the acid generated by the photoacid generator.
In addition, in the second resist composition, an embodiment was described in which two types, a crosslinking agent having a crosslinking group and a compound having a reactive group that reacts with the crosslinking group, are included; It may also be an embodiment containing a reactive group and a reactive group.

The resist composition may include a main chain cleaved polymer and a solvent.
When a polymer is "main chain cleavable", it means that the main chain of the polymer has the property of being cleaved when the polymer is irradiated with light such as ionizing radiation or ultraviolet light.
Examples of main chain cleavage type polymers include acrylic main chain cleavage type resists, such as polymethyl methacrylate (PMMA), ZEP (manufactured by Nippon Zeon Co., Ltd.), which is a copolymer of α-chloromethacrylate and α-methylstyrene. ), and poly 2,2,2-trifluoroethyl α-chloroacrylate (EBR-9, manufactured by Toray Industries, Inc.).

The resist composition may be a so-called metal resist composition.
The metal resist composition includes a photosensitive composition capable of forming a coating containing a metal oxo-hydroxo network having organic ligands through metal carbon bonds and/or metal carboxylate bonds.
Examples of the metal resist composition include the composition described in JP-A-2019-113855, the contents of which are incorporated into the present specification.

The resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total metal element The content is preferably 10 mass ppb or less based on the total mass of the resist composition.

The present invention is basically configured as described above. Although the analysis method, analysis device, chemical solution management method, and resist composition management method of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and may be provided within the scope of the invention. Of course, various improvements or changes may be made.

The features of the present invention will be explained in more detail with reference to Examples below. The materials, reagents, amounts and proportions of substances shown in the following examples, operations, etc. can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.
In this example, the detectable limit standard particle size, repeatability, and measurement time were evaluated.
Examples 1 to 22 and Comparative Examples 1 and 2 will be described below.

(Example 1)
In Example 1, PGMEA (propylene glycol monomethyl ether acetate) was used as a chemical solution, and a dispersion liquid containing commercially available iron oxide particles having a standard particle diameter of 200 nm as standard particles was prepared. In addition, dispersions using PGMEA as the chemical solution and containing commercially available iron oxide particles with a standard particle size of 150 nm as standard particles, dispersions containing commercially available iron oxide particles with a standard particle size of 100 nm as standard particles, and commercially available dispersions containing iron oxide particles with a standard particle size of 100 nm as standard particles; A dispersion containing iron oxide particles with a standard particle size of 75 nm as standard particles, a dispersion containing commercially available iron oxide particles with a standard particle size of 50 nm as standard particles, and a dispersion containing commercially available iron oxide particles with a standard particle size of 25 nm as standard particles. Dispersion containing commercially available iron oxide particles with a standard particle size of 20 nm as standard particles, Dispersion containing commercially available iron oxide particles with a standard particle size of 15 nm as standard particles, Commercially available dispersion containing iron oxide particles with a standard particle size of 10 nm A dispersion liquid containing iron oxide particles as standard particles and a dispersion liquid containing commercially available iron oxide particles having a standard particle diameter of 5 nm as standard particles were prepared.
The standard particle diameter of the commercially available iron oxide particles mentioned above is a value measured using a transmission electron microscope (TEM).

Each dispersion liquid was diluted and adjusted to have approximately 1 particle/cm ² on a silicon substrate with a diameter of 300 mm. The prepared dispersion was applied onto a 300 mm (12 inch) diameter silicon substrate using an electrostatic sprayer. Note that the silicon substrate is a semiconductor substrate.
Further, the total number of metal species to be measured was 30, the number of measurement areas was 2, and the number of metal species to be measured per measurement area on the silicon substrate was 15. Note that the measurement area was divided randomly using pseudorandom numbers.
The metal species to be measured are Li, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Ba, Ta, and W were used.
For the silicon substrate coated with the dispersion liquid, the alignment measuring section acquires the contour information of the surface of the silicon substrate, and then determines the number of metal species, the number of measurement areas, the dividing method, and the metal to be measured per measurement area. The combination data described above was created based on the number of species.
The silicon substrate was transported to the analysis department. A laser ablation ICP mass spectrometry (LA-ICP-MS) device was used in the analysis section. Note that when the silicon substrate was transported to the analysis section, it was transported in a state where it was isolated from the outside air. In the case using the above-mentioned storage container, the silicon substrate was kept isolated from the outside air from beginning to end when the silicon substrate was transported.

In the analysis department, elemental analysis of defects by laser ablation was performed based on the above-mentioned combined data using a laser ablation ICP mass spectrometer having a quadrupole mass spectrometer.
In addition, in the analysis, it was confirmed whether among the metal elements, Fe contained in the standard particles could be detected. We confirmed whether Fe could be detected by replacing the dispersion with a small standard particle size, and determined the size of the standard particle that was the limit for detection. The size of the standard particle at the detectable limit was defined as the "minimum detectable foreign particle size (nm)". The results are shown in Table 1 below.

After determining the detectable limit standard particle size, repeatability was evaluated as follows using a dispersion containing the detectable limit standard particle size.
For evaluation of repeatability, eight silicon substrates were prepared that were coated with a dispersion containing a standard particle size that was at the detectable limit. Using a laser ablation ICP mass spectrometer having the above-mentioned quadrupole mass spectrometer, the number of Fe signals obtained by elemental analysis of defects by laser ablation was measured for each silicon substrate. The standard deviation (3σ) of the number of Fe signals was determined based on the number of Fe signals of the eight silicon substrates.

Note that laser ablation was performed with the silicon substrate housed in the container and with the carrier gas being supplied. An analytical sample obtained by laser ablation was collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry. A femtosecond laser was used for laser ablation.
Argon gas was used as the carrier gas. The flow rate of the carrier gas was 1.69×10 ⁻² Pa·m ³ /sec (10 sccm).
Note that before performing elemental analysis of defects by laser ablation, the inside of the container was cleaned by flushing with a carrier gas.

(Example 2)
Example 2 was the same as Example 1 except that the total number of metal species to be measured was 20 and the number of metal species to be measured per measurement area on the silicon substrate was 15. did.
The metal species to be measured were Li, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, and Y.
(Example 3)
Example 3 was the same as Example 1 except that the total number of metal species to be measured was 10 and the number of metal species to be measured per measurement area on the silicon substrate was 5. did.
The metal species to be measured were Fe, Li, Na, Mg, Al, K, Ca, Sc, Ti, and V.
(Example 4)
Example 4 was the same as Example 1 except that the total number of metal species to be measured was 8 and the number of metal species to be measured per measurement area on the silicon substrate was 4. did.
The metal species to be measured were Fe, Li, Na, Mg, Al, K, Ca, and Ti.
(Example 5)
Example 5 was the same as Example 1 except that the total number of metal species to be measured was 6 and the number of metal species to be measured per measurement area on the silicon substrate was 3. did.
The metal species to be measured were Fe, Li, Na, Mg, Al, and Ti.
(Example 6)
Example 6 was the same as Example 1 except that the total number of metal species to be measured was 4 and the number of metal species to be measured per measurement area on the silicon substrate was 2. did.
The metal species to be measured were Fe, Li, Na, and Ti.
(Example 7)
Example 7 was the same as Example 1 except that the total number of metal species to be measured was 2 and the number of metal species to be measured per measurement area on the silicon substrate was 1. did.
The metal species to be measured were Fe and Ti.

(Example 8)
Example 8 was different from Example 1 except that the total number of metal species to be measured was 5, the number of measurement areas was 5, and the number of metal species to be measured per measurement area on the silicon substrate was 1. The same as in Example 1 was used.
The metal species to be measured were Fe, Li, Na, Mg, and Ti.
(Example 9)
Example 9 was the same as Example 8 except that the method of dividing the measurement area was different. In Example 9, similarly to FIG. 2, the surface of the silicon substrate was divided into five fan-shaped regions having the apex at the center position. The central angle of each region is 72°. In Table 1 below, the mode of region division in Example 9 is described as "cake cutting" in the column of "Measurement region division method."
(Example 10)
Example 10 was the same as Example 8 except that the method of dividing the measurement area was different. In Example 10, similarly to FIG. 3, the silicon substrate was divided into five regions at equal intervals along the diameter direction. In Table 1 below, the mode of region division in Example 10 is described as "vertical division" in the column of "Measurement region division method."

(Example 11)
Example 11 differs from Example 1 in that CHN (propylene glycol monomethyl ether acetate) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and the measurement area was 1 on the silicon substrate. The procedure was the same as in Example 1 except that the number of metal species measured per bump was 1. The metal species to be measured were the same as in Example 3.
(Example 12)
Example 12 differs from Example 1 in that nBA (butyl acetate) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and measurement was performed per measurement area on the silicon substrate. The procedure was the same as in Example 1 except that the number of metal species used was 1. The metal species to be measured were the same as in Example 3.
(Example 13)
Example 13 differs from Example 1 in that PGME (propylene glycol monomethyl ether) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and there was one measurement area on the silicon substrate. The procedure was the same as in Example 1 except that the number of metal species to be measured per hit was 1. The metal species to be measured were the same as in Example 3.

(Example 14)
Example 14 was the same as Example 13 except that a mixed solution of PGMEA and PGME was used as the chemical solution. The mixing ratio of PGMEA and PGME was 40/60 (=PGMEA/PGME) in terms of mass ratio.
(Example 15)
Example 15 was the same as Example 13 except that a mixed solution of PGMEA and PGME was used as the chemical solution. The mixing ratio of PGMEA and PGME was 30/70 (=PGMEA/PGME) in terms of mass ratio.

(Example 16)
Example 16 differs from Example 1 in that EL (ethyl lactate) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and measurement was performed per measurement area on the silicon substrate. The procedure was the same as in Example 1 except that the number of metal species used was 1. The metal species to be measured were the same as in Example 3.
(Example 17)
Example 17 differs from Example 1 in that MIBC (4-methyl-2-pentanol) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and The procedure was the same as in Example 1 except that the number of metal species measured per measurement area was 1. The metal species to be measured were the same as in Example 3.
(Example 18)
Example 18 differs from Example 1 in that IPA (isopropanol) was used as the chemical solution, the total number of metal species to be measured was 10, the number of measurement areas was 10, and measurement was performed per measurement area on the silicon substrate. It was the same as Example 1 except that the number of metal species was 1. The metal species to be measured were the same as in Example 3.

(Example 19)
Example 19 was different from Example 1 except that the total number of metal species to be measured was 3, the number of measurement areas was 3, and the number of metal species to be measured per measurement area on the silicon substrate was 1. The same as in Example 1 was used. The metal species to be measured were Fe, Li, and Ti.
(Example 20)
Example 20 was the same as Example 1 except that the number of measurement areas was 30 and the number of metal species measured per measurement area on the silicon substrate was 1.
(Example 21)
Example 21 was the same as Example 9 except that the method of dividing the measurement area was different. In Example 21, similarly to FIG. 2, the surface of the silicon substrate was divided into five fan-shaped regions having the apex at the center position. When dividing into five fan-shaped regions, the total central angle was set to 360°, and the central angles were randomly set using pseudorandom numbers. In Example 21, the size of the fan-shaped area was not uniform but randomly set. In addition, in Table 1 below, the mode of region division in Example 21 is described as "cake cutting" in the column of "Measurement region division method" as in Example 9.
(Example 22)
Example 22 was the same as Example 3 except that the metal species assigned to the measurement area was different. In Example 22, among the metal species to be measured, Fe, Li, Na, Mg, Al, K, Ca, Sc, Ti, and V, one of the metal species to be measured is Fe, Li, Na, Mg, Al, and K. and Fe, K, Ca, Sc, Ti, and V were assigned to the other measurement region. In this way, two metal types were overlapped, and six metal types were set in each measurement area.

(Comparative example 1)
Comparative Example 1 was the same as Example 1 except that 30 types of metal species were analyzed on the entire surface of the silicon substrate without performing region division.
(Comparative example 2)
Comparative Example 1 was different from Example 1, except that 30 silicon substrates were used and one type of metal species was analyzed on one silicon substrate without performing region division. The same as in Example 1 was used.

As shown in Table 1, Examples 1 to 22, which were divided into multiple regions and assigned a metal type to each region, had a higher number of detectable particles than Comparative Examples 1 and 2, which did not divide the regions. The size was small. Further, in Examples 1 to 22, the measurement time was short, and it was possible to analyze minute defects, and it was also possible to shorten the measurement time.
On the other hand, in Comparative Example 1, many metal species were analyzed over the entire surface of the silicon substrate, so the detection signal level of each metal species was low and the size of detectable particles was large.
In Comparative Example 2, one metal was detected using one silicon substrate, so although the size of the detectable particles was small, the measurement took a long time.
From Examples 1 to 7, even if the area per region is the same, the smaller the total number of metal species to be measured, that is, the larger the measurement area per number of metals to be measured, the larger the detectable particle size. was small.
From Examples 8 to 10, as the area division method, the random method of Example 10 had better repeatability than the regular method of Examples 9 and 10.
From Examples 1 to 22, the larger the area per region, the better the repeatability was.
From Examples 1 to 22, the larger the size of detectable particles, the better the repeatability.

In Examples 1 to 22, the alignment measuring unit acquires the contour information of the surface of the silicon substrate coated with the dispersion liquid, and then the number of metal species, the number of measurement areas, the division method, The above combination data was created based on the number of metal species measured per measurement area. After that, a step of inductively coupled plasma mass spectrometry was carried out, and the above-mentioned series of steps of Examples 1 to 22 were combined with step 1 of setting the number of metal species to be analyzed and dividing the measurement target region of the semiconductor substrate into regions. The same effects as in Examples 1 to 22 can be obtained even if the order of Step 2, Step 3 of assigning a different metal type to each divided region, and Step 4 of performing inductively coupled plasma mass spectrometry is changed. .
In addition, the order of the step 1 of setting the number of metal species to be analyzed, the step 2 of dividing the measurement target region of the semiconductor substrate into regions, and the step 3 of assigning a different metal species to each divided region is as follows: Even if Step 2, Step 1, and Step 3 are replaced in this order, the same effects as in Examples 1 to 22 can be obtained.

10, 10a Analyzer 12a First transfer chamber 12b Measurement chamber 12c Second transfer chamber

12d Analysis chamber

12e Processing chamber 12g Introduction section 12h Wall 13 Storage container 14 Transfer device 14a Mounting section 15 Transfer arm 16 Transfer device 16a Mounting section 20 Alignment measurement Section 22 Stage 23 Light source 24 Imaging section 26 Storage section 27 Calculation section 28 Setting section 29 Input section 30 Analysis section 32 Stage 33 Container section 34 Light source section 35 Condensing lens 36 Analysis unit 37 Drive section 38 Carrier gas supply section 39 Piping 40 Cleaning Gas supply section 41 Outflow section 42 Control section 44 Plasma torch 46 Mass spectrometry section 46a Ion lens section 46b Mass spectrometer section 47 Ion lens 48 Reflectron 49 Detector 50 Semiconductor substrate 50a Surface 51 Defect

51a Analysis sample

52a, 52b, 52c, 52d, 52e, 52f, 52g,

52h Area

53a, 53b, 53c,

53d Area

54a, 54b, 54c, 54d, 54e, 54f Area 70 Contour measuring device C ₁ rotation axis C ₂ rotation axis C ₃ rotation axis H direction La laser Light Ls Light O Center position V Height direction

Claims

A method for analyzing defects located on or inside a semiconductor substrate, the method comprising:
Step 1 of setting the number of metal species to be analyzed;
Step 2 of dividing the measurement target region of the semiconductor substrate into regions;
Step 3 of assigning a different metal type to each of the divided regions;
An analysis method comprising step 4 of irradiating each region with a laser beam, collecting an analysis sample obtained from the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry.
A method for analyzing defects located on or inside a semiconductor substrate, the method comprising:
For the semiconductor substrate, based on setting information including the number of metal species to be analyzed, region division of the measurement target region, and metal species assigned to each of the divided regions,
An analysis method comprising the steps of irradiating each region with a laser beam, collecting an analysis sample obtained from the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry.
The analysis method according to claim 1, further comprising the step of obtaining contour information on the surface of the semiconductor substrate and obtaining information on the measurement target region before the step 2.
The analysis method according to claim 1 or 2, wherein the number of metal species measured per region of the semiconductor substrate is 4 to 10.
The analysis method according to claim 1 or 2, wherein two or three metal species are measured per region of the semiconductor substrate.
The analysis method according to claim 1 or 2, wherein the number of metal species measured per region of the semiconductor substrate is 1.
The analysis method according to claim 1 or 3, wherein step 1 of setting the number of the metal species to be analyzed includes a step of setting the metal species to be analyzed.
The analysis method according to claim 2, wherein the setting information includes information on the metal species to be analyzed.
An apparatus for analyzing defects located on or inside a semiconductor substrate, comprising:
a setting unit that sets the number of metal species to be analyzed, divides the measurement target region of the semiconductor substrate into regions, and assigns a different metal species to each of the divided regions;
An analysis device comprising: an analysis section that irradiates each region with a laser beam, collects an analysis sample obtained from the irradiation with a carrier gas, and performs inductively coupled plasma mass spectrometry.
An apparatus for analyzing defects located on or inside a semiconductor substrate, comprising:
A laser beam is applied to each region of the semiconductor substrate based on setting information including the number of metal species to be analyzed, the division of the measurement target region, and the metal species assigned to each of the divided regions. An analysis device comprising: an analysis section that performs inductively coupled plasma mass spectrometry by collecting an analysis sample obtained from the irradiation with a carrier gas.
The analysis device according to claim 9, further comprising an alignment measurement unit that obtains contour information on the surface of the semiconductor substrate and obtains information on the measurement target region.
The analysis device according to claim 9 or 11, wherein the setting unit sets the number of metal types per region of the semiconductor substrate to 4 to 10.
The analysis device according to claim 9 or 11, wherein the setting unit sets the number of metal types to be hit in one region of the semiconductor substrate to 2 or 3.
The analysis device according to claim 9 or 11, wherein the setting unit sets the hit metal type for one region of the semiconductor substrate to 1.
The analyzer according to claim 9 or 11, wherein the setting section sets the metal species to be analyzed.
The analysis device according to claim 10, wherein the setting information includes information on the metal species to be analyzed.
A method for managing a chemical solution, the method comprising:
A step of bringing the semiconductor substrate into contact with a chemical solution;
a step of setting the number of metal species to be analyzed;
dividing the measurement target region of the semiconductor substrate into regions;
a step of assigning a different metal type to each divided region;
irradiating each region with a laser beam, collecting an analysis sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry;
Comparing the defect mass spectrometry data obtained in the inductively coupled plasma mass spectrometry step with preset reference data to determine whether the mass spectrometry data is within an acceptable range. , How to manage chemical solutions.
A method for managing a chemical solution,
A step of bringing the semiconductor substrate into contact with a chemical solution;
A laser beam is applied to each region of the semiconductor substrate based on setting information including the number of metal species to be analyzed, the division of the measurement target region, and the metal species assigned to each of the divided regions. irradiating the sample, collecting the analytical sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry;
Comparing the defect mass spectrometry data obtained in the inductively coupled plasma mass spectrometry step with preset reference data to determine whether the mass spectrometry data is within an acceptable range. , How to manage chemical solutions.
18. The management of the chemical solution according to claim 17, further comprising the step of obtaining contour information on the surface of the semiconductor substrate and obtaining information on the measurement target region before the step of dividing the measurement target region of the semiconductor substrate into regions. Method.
The method for managing a chemical solution according to claim 17 or 19, wherein the step of setting the number of the metal types to be analyzed includes the step of setting the metal types to be analyzed.
The method for managing a chemical solution according to claim 18, wherein the setting information includes information on the metal species to be analyzed.
A method for managing a resist composition, the method comprising:
applying the resist composition onto a semiconductor substrate;
a step of setting the number of metal species to be analyzed;
dividing the measurement target region of the semiconductor substrate into regions;
a step of assigning a different metal type to each divided region;
irradiating each region with a laser beam, collecting an analysis sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry;
Comparing the defect mass spectrometry data obtained in the inductively coupled plasma mass spectrometry step with preset reference data to determine whether the mass spectrometry data is within an allowable range. , a method for managing resist compositions.
A method for managing a resist composition, the method comprising:
applying the resist composition on a semiconductor substrate;
A laser beam is applied to each region of the semiconductor substrate based on setting information including the number of metal species to be analyzed, the division of the measurement target region, and the metal species assigned to each of the divided regions. irradiating the sample, collecting the analytical sample obtained from the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry;
Comparing the defect mass spectrometry data obtained in the inductively coupled plasma mass spectrometry step with preset reference data to determine whether the mass spectrometry data is within an acceptable range. , a method for managing resist compositions.
23. The resist composition according to claim 22, further comprising the step of obtaining contour information on the surface of the semiconductor substrate to obtain information on the measurement target region before the step of dividing the measurement target region of the semiconductor substrate into regions. management method.
The resist composition management method according to claim 22 or 24, wherein the step of setting the number of the metal species to be analyzed includes the step of setting the metal species to be analyzed.
24. The resist composition management method according to claim 23, wherein the setting information includes information on the metal species to be analyzed.